CN103140136A - Fungicidal pyrazoles and their mixtures - Google Patents

Fungicidal pyrazoles and their mixtures Download PDF

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Publication number
CN103140136A
CN103140136A CN2011800418869A CN201180041886A CN103140136A CN 103140136 A CN103140136 A CN 103140136A CN 2011800418869 A CN2011800418869 A CN 2011800418869A CN 201180041886 A CN201180041886 A CN 201180041886A CN 103140136 A CN103140136 A CN 103140136A
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China
Prior art keywords
compound
fungicide
amine
pyrazoles
dimethyl
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CN2011800418869A
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Chinese (zh)
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CN103140136B9 (en
CN103140136B (en
Inventor
J·K·朗
V·格雷戈里
S·古特里奇
A·E·塔吉
J·F·拜瑞兹耐克
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FMC Corp
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EI Du Pont de Nemours and Co
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Priority to CN201610348850.XA priority Critical patent/CN106417305A/en
Priority to CN201610346618.2A priority patent/CN106008299B/en
Publication of CN103140136A publication Critical patent/CN103140136A/en
Application granted granted Critical
Publication of CN103140136B publication Critical patent/CN103140136B/en
Publication of CN103140136B9 publication Critical patent/CN103140136B9/en
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    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
    • A01N43/56—1,2-Diazoles; Hydrogenated 1,2-diazoles
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C327/00—Thiocarboxylic acids
    • C07C327/38—Amides of thiocarboxylic acids
    • C07C327/40—Amides of thiocarboxylic acids having carbon atoms of thiocarboxamide groups bound to hydrogen atoms or to acyclic carbon atoms
    • C07C327/44—Amides of thiocarboxylic acids having carbon atoms of thiocarboxamide groups bound to hydrogen atoms or to acyclic carbon atoms to carbon atoms of an unsaturated carbon skeleton
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
    • A01N37/34—Nitriles
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
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    • A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
    • A01N37/44—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing at least one carboxylic group or a thio analogue, or a derivative thereof, and a nitrogen atom attached to the same carbon skeleton by a single or double bond, this nitrogen atom not being a member of a derivative or of a thio analogue of a carboxylic group, e.g. amino-carboxylic acids
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
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    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/02—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms
    • A01N43/04—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom
    • A01N43/06—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom five-membered rings
    • A01N43/12—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom five-membered rings condensed with a carbocyclic ring
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    • A01N43/30—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with two or more hetero atoms five-membered rings with two hetero atoms in positions 1,3 with two oxygen atoms in positions 1,3, condensed with a carbocyclic ring
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    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
    • A01N43/40—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
    • A01N43/40—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings
    • A01N43/42—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings condensed with carbocyclic rings
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
    • A01N43/50—1,3-Diazoles; Hydrogenated 1,3-diazoles
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
    • A01N43/54—1,3-Diazines; Hydrogenated 1,3-diazines
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/64—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with three nitrogen atoms as the only ring hetero atoms
    • A01N43/647—Triazoles; Hydrogenated triazoles
    • A01N43/653—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
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    • A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
    • A01N43/74—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,3
    • A01N43/78—1,3-Thiazoles; Hydrogenated 1,3-thiazoles
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    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
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    • A01N43/80—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,2
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
    • A01N43/84—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms six-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,4
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/90—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having two or more relevant hetero rings, condensed among themselves or with a common carbocyclic ring system
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
    • A01N47/10—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof
    • A01N47/12—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof containing a —O—CO—N< group, or a thio analogue thereof, neither directly attached to a ring nor the nitrogen atom being a member of a heterocyclic ring
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
    • A01N47/28—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N<
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    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
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    • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
    • A01N47/28—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N<
    • A01N47/38—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N< containing the group >N—CO—N< where at least one nitrogen atom is part of a heterocyclic ring; Thio analogues thereof
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    • A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
    • A01N59/16—Heavy metals; Compounds thereof
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    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C327/00—Thiocarboxylic acids
    • C07C327/38—Amides of thiocarboxylic acids
    • C07C327/48—Amides of thiocarboxylic acids having carbon atoms of thiocarboxamide groups bound to carbon atoms of six-membered aromatic rings
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    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
    • C07C49/04—Saturated compounds containing keto groups bound to acyclic carbon atoms
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    • C07C49/20—Unsaturated compounds containing keto groups bound to acyclic carbon atoms
    • C07C49/227—Unsaturated compounds containing keto groups bound to acyclic carbon atoms containing halogen
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    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
    • C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
    • C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D231/14—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D231/18—One oxygen or sulfur atom
    • C07D231/20—One oxygen atom attached in position 3 or 5
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    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
    • C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
    • C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D231/14—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D231/38—Nitrogen atoms

Abstract

Disclosed is a fungicidal composition comprising (a) at least one compound selected from the compounds of Formula (1), N-oxides, and salts thereof, wherein R1, R2, R3, R4, R5 and R6 are as defined in the disclosure; and (b) at least one additional fungicidal compound. Also disclosed is a method for controlling plant diseases caused by fungal plant pathogens comprising applying to the plant or portion thereof, or to the plant seed, a fungicidally effective amount of a compound of Formula (1), an N-oxide, or salt thereof (e.g., as a component in the aforesaid composition). Also disclosed is a composition comprising: (a) at least one compound selected from the compounds of Formula (1) described above, N-oxides, and salts thereof; and at least one invertebrate pest control compound or agent.

Description

Antifungal pyrazoles and their mixture
Technical field
The present invention relates to some pyrazole derivatives, their N-oxide and salt, and relate to mixture and the composition that comprises this pyrazol derivatives, and use this pyrazol derivatives and their mixture and composition method as fungicide.
Background technology
For obtaining high crops efficiency, the plant disease that the control plant pathogenic fungi causes is extremely important.To the prejudicial plant disease of ornamental crops, vegetable crop, field crop, cereal and fruit tree crop, can cause output significantly to reduce, thereby cause consumer cost to rise.Except usually having high destructiveness, plant disease also is difficult to control, and can develop the resistance to business fungicide.For this purpose, the commercially available acquisition of many products, but continue to need more effective, more economical, safer or there is the novel Fungicidal compounds of different action sites to environment.Except introducing novel fungicide, the combination of fungicide is normally used for promoting disease to control, to widen control range delaying drug resistance development.In addition, the outstanding combination table of some of fungicide reveals (collaborative) effect that exceeds adduction, thereby the degree of the plant disease control with important commercial value is provided.This area recognizes, the advantage of concrete fungicide combination will be according to following these factors and difference: concrete plant variety and plant disease to be treated and treated plant after still before infection plant's disease fungus.Therefore, need novel favourable combination that multiple choices are provided, farthest to meet concrete plant disease control demand.This type of combination now is found.JP08208620 discloses N-Phenylpyrazole yl amine derivatives as insecticide, weed killer herbicide and fungicide; Yet antifungal pyrazoles of the present invention and their mixture are unexposed in this is announced.
Summary of the invention
The present invention relates to Fungicidal composition (that is, combination), described composition comprises (a) at least one compound, and described compound is selected from compound (comprising all stereoisomers), its N-oxide and salt thereof of formula 1:
Figure BDA00002868169000021
Wherein
X is CHOH, O or NH;
R 1for halogen or methyl;
R 2for H, cyano group, halogen or C 1-C 2alkoxyl;
R 3for H, halogen or methyl;
R 4for halogen;
R 5for H, cyano group, halogen or C 1-C 2alkoxyl; And
R 6for H or halogen; With
(b) at least one additional Fungicidal compounds.
The invention still further relates to composition, described composition comprises: (a) at least one compound, and described compound is selected from compound, its N-oxide and salt thereof of formula 1 mentioned above; Control compound or reagent with at least one invertebrate pests.
The invention still further relates to a kind of composition comprised in above-mentioned composition, described foregoing comprises component (a) and at least one annexing ingredient, and described annexing ingredient is selected from surfactant, solid diluent and liquid diluent.
The invention still further relates to for controlling the method for the plant disease caused by plant pathogenic fungi, described method comprises to plant or its part or uses a kind of in the above-mentioned composition of antifungal effective dose to plant seed.
Preceding method also can be described as the method for the disease that protective plant or plant seed avoid being caused by fungal pathogens; described method comprises to plant (or its part) or plant seed uses a kind of (be applied directly on plant or plant seed, or for example, use by environment (somatomedin)) in the above-mentioned composition of antifungal effective dose.
The invention still further relates to compound or its N-oxide or its salt of above-mentioned formula 1.The invention still further relates to Fungicidal composition, the compound that described composition comprises formula 1 or its N-oxide or its salt and at least one annexing ingredient, described annexing ingredient is selected from surfactant, solid diluent and liquid diluent.The present invention and relate to protective plant or the method for the disease that plant seed is avoided being caused by fungal pathogens, described method comprises compound or its N-oxide or its salt of using the formula 1 of antifungal effective dose to plant or plant seed.
Embodiment
As used herein, term " comprises ", " comprising ", " including ", " containing ", " having ", " containing ", " containing ", " holding ", " being characterised in that " or its any other modification are intended to contain comprising of nonexcludability, with any condition that is defined as clearly indicated.For example, the composition that comprises series of elements, mixture, technique or method needn't only limit to those elements, but can comprise other element of clearly not listing, or other intrinsic element of such composition, mixture, technique or method.
Conjunctive phrase " by ... form " do not comprise any unspecified element, step or composition.If in the claims, this type of word restriction claim, be not described those material not comprise the impurity except usually following with it.When phrase " by ... form " appear in the clause of claim main body, rather than immediately after preface, it only limits the element of describing in this clause; Other element is not excluded outside claim as a whole.
Conjunctive phrase " basically by ... form " for limiting composition or method; described composition or method are except literal those disclosed; also comprise material, step, parts, component or element; precondition is that these additional materials, step, parts, component or element do not affect essential characteristic of the present invention and one or more novel features that is subject to claims protection to a great extent.Term " basically by ... form " occupy the centre of " comprising " and " by ... composition ".
When the applicant has used open-ended term as " comprising " defined the present invention or its part, should should be readily appreciated that (except as otherwise noted), specification should be interpreted as also using term " basically by ... form " or " by ... form " the present invention described.
In addition, unless contrary clearly stating arranged, "or" refers to the "or" of inclusive, rather than refers to the "or" of exclusiveness.For example,, any one all mean to satisfy condition A or B:A are that genuine (or existence) and B are that false (or non-existent), A are that false (or non-existent) and B are that genuine (or existence) and A and B are genuine (or existence).
Equally, relate to element or component illustration (occur) number of times to be positioned at that indefinite article " " before element of the present invention or component or " a kind of " be intended to be nonrestrictive.Therefore, " one " or " a kind of " should be interpreted as and comprise one or at least one, and the word singulative of element or component also comprises plural form, unless there is numeral obviously to mean odd number.
Described in as open as the present invention and claim, " plant " comprises the member of vegetative kingdom of all life stages, especially spermatophyte (gymnosperm), described life stage comprises plant juvenile stage (seed development of for example germinateing becomes rice shoot) and ripe breeding stage (plant that for example blooms and produce seeds).Plant part comprises that the geotropism part for example usually be grown in, below growth medium (soil) surface is such as root, stem tuber, bulb and bulb, and the part of growing more than somatomedin such as leaf (comprising stem and leaf), flower, fruit and seed.
As described herein, use separately or refer to the plant young by the seed embryonic development with the term " rice shoot " that word is used in combination.
In above describing in detail, term " alkoxyl " comprises for example methoxyl group and ethyoxyl.Term " halogen " comprises fluorine, chlorine, bromine or iodine.
The total number of carbon atoms in substituting group is by " C i-C j" prefix designates, the number that wherein i and j are 1 to 2.
The compound relevant with method of the present invention to composition can exist by one or more stereoisomers.Multiple stereoisomer comprises enantiomer, diastereomer, atropisomer and geometric isomer.One skilled in the art will appreciate that when a kind of stereoisomer during with respect to other stereoisomer enrichment, or, when it separates with other stereoisomer, it may more have activity and/or may show useful effect.In addition, skilled in the art will recognize that how to separate, enrichment and/or optionally prepare described stereoisomer.Compound in the present composition can be used as the mixture of stereoisomer, independent stereoisomer or exists as the form of optically active.
Synthetic method for the preparation of the heterocycle N-oxide such as pyrazoles is well known to those skilled in the art, comprises and uses peroxy acid (as peracetic acid and metachloroperbenzoic acid (MCPBA)), hydrogen peroxide, alkyl hydroperoxide (as tert-butyl hydroperoxide), sodium perborate and bisoxirane (as dimethyldioxirane) oxygenated heterocyclic.These methods of preparation N-oxide have been widely described and have summarized in document, referring to for example: the Comprehensive Organic Synthesis of T.L.Gilchrist, the 7th volume, the 748-750 page, S.V.Ley edits, Pergamon Press; The Comprehensive Heterocyclic Chemistry of M.Tisler and B.Stanovnik, the 3rd volume, the 18-20 page, A.J.Boulton and A.McKillop edit, Pergamon Press; The Advances in Heterocyclic Chemistry of M.R.Grimmett and B.R.T.Keene, the 43rd volume, the 149-161 page, A.R.Katritzky edits, Academic Press; The Advances in Heterocyclic Chemistry of M.Tisler and B.Stanovnik, the 9th volume, the 285-291 page, A.R.Katritzky and A.J.Boulton edit, Academic Press; And the Advances in Heterocyclic Chemistry of G.W.H.Cheeseman and E.S.G.Werstiuk, the 22nd volume, the 390-392 page, A.R.Katritzky and A.J.Boulton edit, Academic Press.
Those skilled in the art recognizes, due to the salt of compound under environment and physiological condition and their corresponding salt-independent shapes, in balance, so salt is shared biological use with salt-independent shape.Therefore, separately and the various salt of the compound of the formula in mixture 1 can be used for the plant disease that control causes by plant pathogenic fungi (be applicable to agronomy).The salt of the compound of formula 1 comprises the acid-addition salts formed with inorganic acid or organic acid, and described acid is as hydrobromic acid, hydrochloric acid, nitric acid, phosphoric acid, sulfuric acid, acetic acid, butyric acid, fumaric acid, lactic acid, maleic acid, malonic acid, oxalic acid, propionic acid, salicylic acid, tartaric acid, 4-toluenesulfonic acid or valeric acid.Therefore, the present invention relates to the mixture of compound, described compound is selected from the upper suitable salt of formula 1, its N-oxide and agricultural thereof.
Be selected from the compound of formula 1, its stereoisomer, dynamic isomer, N-oxide and salt usually to exist more than a kind of form, and therefore formula 1 comprises all crystallizations of formula 1 expression and the compound of noncrystalline form.Noncrystalline form is included as the embodiment of solid as wax and natural gum, and is that the embodiment of liquid is as solution and fused mass.Crystal form comprises and represents basically the embodiment of single crystal form body and the embodiment that represents polymorphs body (being different crystal forms) mixture.Term " polymorphs body " relates to the concrete crystal formation of compound that can the different crystal forms crystallization, and these crystal formations have different molecules align and/or conformation in lattice.Although polymorphs body can have identical chemical composition, they also can have different compositions, and this should be decided by whether to exist faint or powerful water or other molecule that is bonded to intracell cocrystallization.Polymorphs body can have different chemistry, physics and biological nature, as crystal form, density, hardness, color, chemical stability, fusing point, hygroscopicity, suspendability, dissolution rate and bioavilability.Those skilled in the art will know, another kind of polymorphs body or polymorphs body mixture with respect to the same compound meaned by formula 1, the polymorphs body of the compound meaned by formula 1 can demonstrate beneficial effect (suitability that for example prepares useful formulations, the biological property through improving).Preparation can realize by method known to those skilled in the art with the specific polymorphs body that separates the compound meaned by formula 1, comprise and for example adopt selected solvent and temperature to carry out crystallization.
As described in summary of the invention, one aspect of the present invention relates to composition, and described composition comprises (a) at least one compound, and described compound is selected from formula 1, its N-oxide and salt thereof, and (b) at least one additional Fungicidal compounds.More specifically, component (b) is selected from
(b1) benzimidazole methyl carbamate (MBC) fungicide;
(b2) dicarboximide fungicide;
(b3) demethylation inhibitor (DMI) fungicide;
(b4) phenyl amide fungicide;
(b5) amine/morpholine fungicide;
(b6) phosphatide biosynthesis inhibitor fungicide;
(b7) carboxylic acid amides fungicide;
(b8) hydroxyl (2-amino-) pyrimidine fungicide;
(b9) aniline pyrimidine fungicide;
(b10) N-carbanilate fungicide;
(b11) outside inhibitor (QoI) fungicide of quinone;
(b12) phenylpyrrole fungicide;
(b13) quinoline fungicide;
(b14) class lipid peroxidation inhibitor fungicide;
(b15) melanocyte biosynthesis inhibitor-reductase (MBI-R) fungicide;
(b16) melanocyte biosynthesis inhibitor-dehydratase (MBI-D) fungicide;
(b17) hydroxyanilines fungicide;
(b18) squalene-inhibitors of cyclooxygenases fungicide;
(b19) polyoxin fungicide;
(b20) phenylurea fungicide;
(b21) inner inhibitor (QiI) fungicide of quinone;
(b22) benzamide fungicide;
(b23) enol pyranose aldehydic acid antibiotic fungicide;
(b24) own pyrans glycosyl antibiotic fungicide;
(b25) glycopyranosyl antibiotic: protein synthesis of antifungal agents;
(b26) glycopyranosyl antibiotic: trehalase and inositol biosynthesis fungicide;
(b27) cyanoacetamide oxime fungicide;
(b28) carbamate fungicide;
(b29) the even fungicide of oxidative phosphorylation solution;
(b30) organotin fungicide;
(b31) carboxylic acid fungicide;
(b32) heteroaromatic fungicide;
(b33) phosphonate ester fungicide;
(b34) phthalamidic acid fungicide;
(b35) phentriazine fungicide;
(b36) benzene-sulfonamide fungicide;
(b37) pyridazinone fungicide;
(b38) thiophene-carboxylic acid amides fungicide;
(b39) pyrimidine acid amides fungicide;
(b40) carboxylic acid amide (CAA) fungicide;
(b41) tetracycline antibiotic fungicide;
(b42) thiocarbamate fungicide;
(b43) benzamide fungicide;
(b44) host plant defence induction type fungicide;
(b45) multidigit point contact active fungicide;
(b46) fungicide, described fungicide is not the fungicide of component (a) and component (b1) to (b45); And
(b1) to the salt of the compound of (b46).
It should be noted that in an embodiment, component (b) comprises at least one Fungicidal compounds, and described Fungicidal compounds is from being selected from (b1) to (b46) two not each group on the same group.
" benzimidazole methyl carbamate (MBC) fungicide (b1) " (bactericide resistance Action Committee (FRAC) encodes 1) is by being combined to suppress mitosis with 'beta '-tubulin at the microtubule assembly process.Suppress the microtubule assembling and can upset cell division, the transmission in cell and cell structure.Benzimidazole methyl carbamate fungicide comprises benzimidazole and topsin fungicide.Benzimidazole comprises benomyl, carbendazim, furidazol and probenazole.The topsin class comprises topsin and thiophanate-methyl.
" dicarboximide fungicide (b2) " (FRAC coding 2) is intended to by disturbing the NADH Cytochrome c reductase to carry out the class lipid peroxidation in Antifungi.Example comprises chlozolinate, iprodione, procymidone and vinclozolin.
" demethylation inhibitor (DMI) fungicide (b3) " (FRAC coding 3) is suppressed at the C14-demethylase worked in the sterol preparation.Sterol such as ergosterol is that membrane structure and function are required, and making them is that generation functional cell wall institute is requisite.Therefore, contact with these fungicides and cause sensitization fungi misgrowth and final dead.DMI fungicide is divided into the number of chemical classification: azole (comprising triazole type and imidazoles), miazines, piperazines and pyridines.Triazole type comprises penta ring azoles, Bitertanol, bromuconazole, Cyproconazole, Difenoconazole, alkene azoles alcohol (comprising alkene azoles alcohol-M), epoxiconazole, etaconazole, RH-7592, Fluquinconazole, Flusilazole, Flutriafol, own azoles alcohol, acid amides azoles, plants bacterium azoles, metconazole, nitrile bacterium azoles, penconazole, propiconazole, prothioconazoles, quinoline azoles, simeconazoles, Tebuconazole, fluorine ether azoles, triazolone, Triadimenol, triticonazole and uniconazole P.Imidazoles comprise clotrimazole, econazole, imazalil, Isoconazole, Miconazole, imidazoles, Prochloraz, pefurazoate and fluorine bacterium azoles.Miazines comprises Fenarimol, nuarimol and triarimol.Piperazines comprises triforine.Pyridines comprises fourth Saite and pyrifenox.The biochemistry investigation has shown that all above-mentioned fungicide is DMI fungicide, as by people such as K.H.Kuck at Modern Selective Fungicides-Properties, Applications and Mechanisms of Action, H.Lyr(edits) Gustav FischerVerlag:New York, 1995,205-258) described in.
" phenyl amide fungicide (b4) " (FRAC coding 4) is the special inhibitor of RNA polymerase in the oomycetes fungi.The sensitization fungi contacted with these fungicides demonstrates the decline of the urine nucleosides being introduced to the ability in rRNA.By contacting with this fungicide, can stop the advolution of sensitization fungi.Phenyl amide fungicide comprise the acyl group alanine,
Figure BDA00002868169000091
oxazolidone and butyrolactone fungicide.Described acyl group alanine comprises that M 9834, M 9834-M, furalaxyl, metalaxyl, metalaxyl-M(also are known as metalaxyl). (oxazolidinon-5-yl-methyl)-2-thiophene-carboxamides comprises Wakil.Butyrolactone comprises ofurace.
(b5) " amine/morpholine fungicide " (FRAC coding 5) suppresses two target sites in the sterol biosynthesis approach, Δ 8→ Δ 7isomerase and Δ 14reductase.Sterol such as ergosterol is that membrane structure and function are required, and making them is that generation functional cell wall institute is requisite.Therefore, it contacts with these fungicides and causes sensitization fungi misgrowth and final dead.Amine/morpholine fungicide (also being called as non--DMI sterol biosynthesis inhibitor) comprises morpholine, piperidines and spiroketal-amine fungicide.The morpholine class comprises cartap, dodemorph, butadiene morpholine, tridemorph and Trimorfamid Fademorf.Piperidines comprises fenpropidin and pipron.Spiroketal-amine comprises volution bacterium amine.
" phosphatide biosynthesis inhibitor fungicide (b6) " (FRAC coding 6) carrys out the growth of Antifungi by affecting the phosphatide biosynthesis.Phosphatide biosynthesis fungicide comprises thiophosphate and dithiolane fungicide.Group thiophosphate comprises edifenphos, iprobenfos and Ppyrazophos.The dithiolane class comprises Isoprothiolane.
" carboxylic acid amides fungicide (b7) " (FRAC coding 7) suppresses the breathing of Complex II (succinate dehydrogenase) fungi by upsetting the key enzyme that is called succinate dehydrogenase in Cray Bai Shi circulation (TCA circulation).Suppress breathing and can stop fungi to produce ATP, thereby suppress Growth and reproduction.Carboxylic acid amides fungicide comprises benzamide, furancarboxamide, oxathiin carboxylic acid amides, thiazole carboxylic acid amides, pyrazoles carboxylic acid amides and pyridine carboxamides.Benzamides comprises benodanil, flutolanil and mebenil.The furancarboxamide class comprises first furan anilide.The oxathiin carboxyl acylamide comprises carboxin and oxycarboxin.The thiazole carboxyl acylamide comprises that the thiophene furan goes out.Described pyrazoles carboxyl acylamide comprises wide-spectrum bactericide, good fortune Lapie, naphthalene pyrrole bacterium amine (isopyrazam), fluorobenzene pyrrole bacterium amine (fluxapyroxad), pyrrole metsulfovax, encircles the third pyrrole bacterium amine (sedaxane) (N-[2-(1S, 2R)-[1,1'-joins cyclopropane]-2-base phenyl]-the 3-(difluoromethyl)-1-methyl isophthalic acid H-pyrazole-4-carboxamide) and penta benzene pyrrole bacterium amine (penflufen) (N-[2-(1, the 3-dimethylbutyl) phenyl]-5-is fluoro-1,3-dimethyl-1H-pyrazole-4-carboxamide) (the PCT patent is announced WO2003/010149).The pyridine carboxamides class comprises Boscalid.
" hydroxyl (2-amino-) pyrimidine fungicide (b8) " (FRAC coding 8) is synthetic by disturbing adenosine deaminase to suppress nucleic acid.Example comprises the phonetic phenol of bupirimate, Milcurb and second.
" aniline pyrimidine fungicide (b9) " (FRAC coding 9) is intended to suppress the biosynthesis of amino acids methionine, and is intended to block the secretion of the infective stage hydrolase that decomposes of chien shih plant cell.Example comprises cyprodinil, Pai Lin and phonetic mould amine go out.
" N-carbanilate fungicide (b10) " (FRAC coding 10) is by being combined with 'beta '-tubulin and upsetting microtubule and assemble to suppress mitosis.Suppress the microtubule assembling and can upset cell division, the transmission in cell and cell structure.Example comprises the mould prestige of second.
" outside inhibitor (QoI) fungicide (b11) of quinone " (FRAC coding 11) carrys out the mitochondrial breathing of Complex II I in Antifungi by affecting the panthenol oxidase.The oxidation of panthenol is being arranged in the cytochrome b c of fungi mitochondrial inner membrane 1" quinone outside " (Q of compound o) site is blocked.Suppress mitochondrial respiratory and can stop fungi normal growth and development.The outside inhibitor fungicide of quinone comprises methoxy acrylate, methoxyl group carbamate, oximide acetic acid ester, oximinoacetamide and dihydro two
Figure BDA00002868169000101
piperazine fungicide (jointly also being known as methoxy acrylate fungicide) and
Figure BDA00002868169000102
oxazolidinedione, imidazolone and benzylamino formic acid esters fungicide.Methoxy acrylic comprises Fluoxastrobin, Enestroburin (SYP-Z071) and ZEN 90160.The methoxyl group carbamate comprises pyraclostrobin and azoles amine bacterium ester.The oximide acetic acid ester comprises that gram receives glad, azoles bacterium ester and oxime bacterium ester.The oximinoacetamide class comprises dimoxystrobin, SSF 126, orysastrobin and α-(methoxyimino)-N-methyl-2-[[[1-[3-(trifluoromethyl) phenyl] ethyoxyl] imino group] methyl] phenyl acetamide.Dihydro two
Figure BDA00002868169000103
the piperazine class comprises fluoxastrobin.
Figure BDA00002868169000104
the oxazolidinedione class comprises
Figure BDA00002868169000105
cycloheximide triazole.Imidazolone type comprises Fenamidone.The benzylamino formate ester comprises pyrrole bacterium benzene prestige (pyribencarb).
The MAP protein kinase relevant to the infiltration signal transduction in " phenylpyrrole fungicide (b12) " (FRAC coding 12) Antifungi.Fenpiclonil and fludioxonil are the examples of this fungicide.
" quinoline fungicide (b13) " (FRAC coding 13) is intended to carry out the Inhibitory signal transduction by affecting early stage cell signal G-albumen.Show, they can disturb the fungi that causes the powdery mildew disease to produce and/or the formation of appresorium.Fast promise sweet smell is the example of this type of fungicide.
The film that " class lipid peroxidation inhibitor fungicide (b14) " (FRAC coding 14) is intended to by affecting in fungi synthesizes to suppress the class lipid peroxidation.This class members such as Grandox fumigant also can affect other bioprocess, such as breathing and the melanocyte biosynthesis.Class lipid peroxidation fungicide comprises aromatic hydrocarbons and 1,2,4-thiadiazoles fungicide.Aromatic hydrocarbons comprises biphenyl, chloroneb, botran, pcnb, tecnazene and tolelofos-methyl.1,2,4-thiadiazole comprises Grandox fumigant.
" melanocyte biosynthesis inhibitor-reductase (MBI-R) fungicide (b15) " (FRAC coding 16.1) suppresses the naphthal reduction step in the melanocyte biosynthesis.Melanocyte is that some fungal infection host plant is necessary.Melanocyte biosynthesis inhibitor-reductase fungicide comprises isobenzofuranone, pyrrolo-quinolone and triazol benzthiazole fungicides.Isobenzofuran ketone comprises Rabcide.The pyrrolo-quinolones comprises pyroquilon.The triazol benzothiazoles comprises tricyclazole.
" melanocyte biosynthesis inhibitor-dehydratase (MBI-D) fungicide (b16) " (FRAC coding 16.2) can suppress the pillar spore ketone dehydratase in the melanocyte biosynthesis.Melanocyte is that some fungal infection host plant is necessary.Melanocyte biosynthesis inhibitor-dehydratase fungicide comprises cyclopropane carboxamide, carboxylic acid amides and propionamide fungicide.The cyclopropane carboxamide class comprises ring propionyl bacterium amine.Carboxyl acylamide comprises two chlorine zarilamids.Propionamides comprises zarilamid.
" hydroxyanilines fungicide (b17) " (FRAC coding 17) is suppressed at the C4-demethylase worked in the sterol preparation.Example comprises fenhexamid.
" squalene-inhibitors of cyclooxygenases fungicide (b18) " (FRAC coding 18) suppresses the squalene-epoxidase in the ergosterol biosynthesis pathway.Sterol is as ergosterol is that membrane structure and function are required, and making them is that generation functional cell wall is necessary.Therefore, it contacts with these fungicides and causes sensitization fungi misgrowth and final dead.Squalene-inhibitors of cyclooxygenases fungicide comprises thiocarbamate and allylamine fungicide.Thiocarbamates comprises pyributicarb.Propylamine comprises how replacing sweet smell and Terbinafine.
" polyoxin fungicide (b19) " (FRAC coding 19) suppresses the chitin synthase.Example comprises polyoxin.
" phenylurea fungicide (b20) " (FRAC coding 20) is intended to affect the cell plant division.Example comprises Pencycuron.
" inner inhibitor (QiI) fungicide (b21) of quinone " (FRAC coding 21) carrys out the Complex II I mitochondrial respiratory in Antifungi by affecting the panthenol reductase.The reduction of panthenol is being arranged in the cytochrome b c of fungi mitochondrial inner membrane 1" quinone inside " (Q of compound i) site is blocked.Suppress mitochondrial respiratory and can stop fungi normal growth and development.The inner inhibitor fungicide of quinone comprises cyano group imidazoles and sulfonamides triazole antifungal agents.The cyano group imidazoles comprises that the match seat goes out.The sulfonamides triazole type comprises amisulbrom.
" benzamide fungicide (b22) " (FRAC coding 22) is by being combined with 'beta '-tubulin and upsetting microtubule and assemble to suppress mitosis.Suppress the microtubule assembling and can upset cell division, upset the transmission in cell and cell structure.Example comprises oxamides.
" enol pyranose aldehydic acid antibiotic fungicide (b23) " (FRAC coding 23) carrys out the Antifungi growth by affecting the protein biosynthesis.Example comprises blasticidin S-S.
" own pyrans glycosyl antibiotic fungicide (b24) " (FRAC coding 24) carrys out the Antifungi growth by affecting the protein biosynthesis.Example comprises kasugarnycin.
" the glycopyranosyl antibiotic: " protein synthesis of antifungal agents (b25) " (FRAC coding 25) carrys out the Antifungi growth by affecting the protein biosynthesis.Example comprises streptomycin.
" glycopyranosyl antibiotic: trehalase and creatase biosynthesis fungicide (b26) " (FRAC coding 26) suppresses the trehalase in the inositol biosynthesis pathway.Example comprises jinggangmeisu.
" cyanoacetamide oxime fungicide (b27) " (FRAC coding 27) comprises white urea cyanogen.
" carbamate fungicide (b28) " (FRAC coding 28) is considered to conk multiaction point inhibitor.They are intended to the synthetic of fatty acid in the interference cell film, thereby upset cell membrane permeability.Propamocarb, iodo propinyl butyl carbamate and prothiocarb are the examples of this type of fungicide.
" the even fungicide (b29) of oxidative phosphorylation solution " (FRAC coding 29) breathed in Antifungi by separating even oxidative phosphorylation.Suppress to breathe and can stop fungi normal growth and development.This type of comprises that 2,6-dinitroaniline such as fluazinam, pyrimidone hydrazone class such as ferimzone and crotonic acid dinitro phenyl ester class are such as karathane, dinocap and binapacryl.
" organotin fungicide (b30) " (FRAC coding 30) suppresses adenosine triphosphate adenosine monophosphate (ATP) synthase in the oxidative phosphorylation approach.Example comprises fentin acetate, triphenyl tin chloride and triphenyl tin hydroxide.
" carboxylic acid fungicide (b31) " (FRAC coding 31) carrys out the Antifungi growth by affecting DNA (deoxyribonucleic acid) (DNA) II type topoisomerase (gyrase).Example comprises
Figure BDA00002868169000121
quinoline acid.
" heteroaromatic fungicide (b32) " (FRAC coding 32) is intended to affect the synthetic of DNA/ ribonucleic acid (RNA).Heteroaromatic fungicide comprises different
Figure BDA00002868169000122
azoles and isothiazoline one fungicide.Different
Figure BDA00002868169000123
azole comprises dislikes mould spirit, and isothiazolinone comprises octhilinone.
" phosphonate ester fungicide (b33) " (FRAC coding 33) comprises phosphorous acid and various salt thereof, comprises phosethyl-Al.
" phthalamidic acid fungicide (b34) " (FRAC coding 34) comprises tecloftalam.
" phentriazine fungicide (b35) " (FRAC coding 35) comprises azoles bacterium piperazine.
" benzene-sulfonamide fungicide (b36) " (FRAC coding 36) comprises flusulfamide.
" pyridazinone fungicide (b37) " (FRAC coding 37) comprises diclomezine.
" thiophene-carboxylic acid amides fungicide (b38) " (FRAC coding 38) is intended to affect the formation of ATP.Example comprises Silthiopham.
" pyrimidine acid amides fungicide (b39) " (FRAC coding 39) carrys out the Antifungi growth by affecting the phosphatide biosynthesis, and comprises the difluoro woods.
" carboxylic acid amide (CAA) fungicide (b40) " (FRAC) encodes 40) be intended to suppress phosphatide biosynthesis and cell wall deposition.The inhibitory action of these processes has stoped the growth of target fungi and has caused its death.Carboxylic acid amide fungicide comprises cinnamamide, figured silk fabrics amine amide carbamate and mandelic acidamide fungicide.Cinnamide comprises dimethomorph and flumorph.Described figured silk fabrics amine amide carbamates comprises that benzene metsulfovax, cumene metsulfovax, Propineb and downy mildew go out.Mandelic acidamide comprises mandipropamid, N-[2-[4-[[3-(4-chlorphenyl)-2-propine-1-yl] the oxygen base]-the 3-methoxyphenyl] ethyl]-3-methyl-2-[(methyl sulphonyl) amino] butyramide and N-[2-[4-[[3-(4-chlorphenyl)-2-propine-1-yl] the oxygen base]-the 3-methoxyphenyl] ethyl]-3-methyl-2-[(ethylsulfonyl) amino] butyramide.
" tetracycline antibiotic fungicide (b41) " (FRAC coding 41) carrys out the Antifungi growth by affecting compound 1 NADH (NADH) oxidoreductase.Example comprises oxytetracycline.
" thiocarbamate fungicide (b42) " (FRAC coding 42) comprises methasulfocarb.
" benzamide fungicide (b43) " (FRAC coding 43) is by making class spectrin delocalization carry out the Antifungi growth.Example comprises fluopicolide fungicide, such as fluopicolide and fluorine pyrrole bacterium acid amides.
" host plant defence induction type fungicide (b44) " (FRAC encode P) induces the host plant defense mechanism.Host plant defence induction type fungicide comprises diazosulfide, benzisothiazole and thiadiazoles-carboxylic acid amides fungicide.The diazosulfide class comprises my acid benzene-S-methyl.Benzo isothiazole comprises allyl isothiazole.Thiadiazoles-carboxyl acylamide comprises tiadinil and isotianil.
" multidigit point-contact type fungicide (b45) " is by the growth of multidigit point effect Antifungi and have contact/prophylactic activity.This type of fungicide comprises: " copper fungicide agent (b45.1) (FRAC encode M1) ", " sulphur fungicide (b45.2) (FRAC encode M2) ", " dithiocarbamate fungicide (b45.3) (FRAC encode M3) ", " phthalimide fungicide (b45.4) (FRAC encode M4) ", " chlorine nitrile fungicide (b45.5) (FRAC encode M5) ", " sulphamide fungicide (b45.6) (FRAC encode M6) ", " guanidine fungicide (b45.7) (FRAC encode M7) " " triazine fungicide (b45.8) (FRAC encode M8) " and " quinone fungicide (b45.9) (FRAC encode M9) "." copper fungicide agent " is the inorganic compound that comprises copper, is generally copper (II) oxidation state; Example comprises Cupravit, copper sulphate and Kocide SD, comprises the composition such as bordeaux mixture (ternary copper sulphate)." sulphur fungicide " is for comprising ring with sulphur atom or the inorganic compound of chain; Example comprises elementary sulfur." dithiocarbamate fungicide " comprises the dithiocarbamate molecular moiety; Example comprises mancozeb, Carbatene, Propineb, ferbam, maneb, arasan, zineb and ziram." phthalimide fungicide " comprises phthalimide quasi-molecule cryptogam; Example comprises folpet, captan and difoltan." chlorine nitrile fungicide " comprises by the aromatic ring of chlorine and cyano group replacement; Example comprises tpn." sulfonamide fungicide " comprises Euparen and tolyfluanid." guanidine fungicide " comprises dodine, gram heat is clean and iminoctadine." triazine fungicide " comprises anilazine." quinone fungicide " comprises the Delan.
" fungicide, described fungicide is not the fungicide of component (a) and component (b1) to (b45); (b46) " comprise the fungicide that some its binding mode may be unknown.These comprise: (b46.1) " thiazole carboxylic acid amides fungicide " (FRAC encode U5), (b46.2) " phenyl-acetamides fungicide " (FRAC encode U6), (b46.3) " quinazolinone fungicide " (FRAC encode U7), (b46.4) " benzophenone fungicide " (FRAC encode U8) and (b46.5) " triazolopyrimidinyl amines fungicide " (FRAC coding 45).The thiazole carboxyl acylamide comprises Guardian.The phenylacetyl amine comprises cyflufenamid and N-[[(cyclo propyl methoxy) amino] [the 6-(difluoro-methoxy)-2, the 3-difluorophenyl]-methylene] phenyl acetamide.Quinazolinones comprises the third oxygen quinoline and the iodo-3-propyl group of 2-butoxy-6--4H-1-benzopyran-4-one.Described benzophenone comprises metrafenone and methoxy benzene pyridine bacterium (pyriofenone).Described triazolopyrimidinyl amines comprises benzene azoles mepanipyrim, and it is believed that by ubiquinone-cytochrome b c1 reductase, in conjunction with undefined site, suppressing the effect of compound III mitochondrial respiratory.Described (b46) class also comprises diclomezin, Xin Asu benevolence (ferric methylarsonate), amine benzene pyrrole bacterium ketone (fenpyrazamine), pyrrolnitrin, chinomethionat, isobutyl ethoxyquin (tebufloquin), the fluoro-5-(trifluoromethyl of 2-[[2-) phenyl] sulfo-]-the 2-[3-(2-anisyl)-the inferior thiazolidinyl of 2-] acetonitrile, 3-[5-(4-chlorphenyl)-2,3-dimethyl-3-is different
Figure BDA00002868169000151
azoles quinoline base] pyridine, N-[1-[[[1-(4-cyano-phenyl) ethyl] sulfonyl] methyl] propyl group] carbamic acid-4-fluorobenzene ester, the chloro-6-(2 of 5-; 4; the 6-trifluorophenyl)-7-(4-methyl piperidine-1-yl) [1; 2; 4] triazol [1; 5-a] pyrimidine, the chloro-2-nitrobenzophenone of N-(4-)-N-ethyl-4-Methyl benzenesulfonyl ammonia, the chloro-3-(trifluoromethyl of N'-[4-[4-) phenoxy group]-2, the 5-3,5-dimethylphenyl]-N-ethyl-N-methyl azomethine acid amides and 1-[(2-propylene sulfenyl) carbonyl]-the 2-(1-Methylethyl)-the 4-(2-aminomethyl phenyl)-5-amino-1H-pyrazoles-3-ketone.
" fungicide, described fungicide is not the fungicide of component (a) and component (b1) to (b45); (b46) " also comprise (b46.5) 6-quinolyl oxygen yl acetamide compound and the salt thereof of formula A1
Figure BDA00002868169000152
Wherein
R a1for halogen, C 1-C 4alkoxyl or C 1-C 4alkynyl;
R a2for H, halogen or C1-C 4alkyl;
R a3for C 1-C 12alkyl, C 1-C 12haloalkyl, C 1-C 12alkoxyl, C 2-C 12alkoxyalkyl, C 2-C 12thiazolinyl, C 2-C 12alkynyl, C 4-C 12alkoxyl thiazolinyl, C 4-C 12alkoxyl alkynyl, C 1-C 12alkylthio group or C 2-C 12alkylthio alkyl;
R a4for methyl or Y a1-R a5;
R a5for C 1-C 2alkyl; And
Y a1for CH 2, O or S.
The compound of formula A1, they are generally known as the purposes of fungicide and the method for preparation; Announce WO2004/047538, WO2004/108663, WO2006/058699, WO2006/058700, WO2008/110355, WO2009/030469, WO2009/049716 and WO2009/087098 referring to for example PCT patent.The example of the compound of formula A1 comprises: the bromo-6-quinolyl of 2-[(3-) oxygen]-N-(1, 1-dimethyl-2-butine-1-yl)-2-(methyl mercapto) acetamide, 2-[(3-acetenyl-6-quinolyl) oxygen]-the N-[1-(methylol)-1-methyl-2-propine-1-yl]-the 2-(methyl mercapto) acetamide, N-(1, 1-dimethyl-2-butine-1-yl)-2-[(3-acetenyl-6-quinolyl) oxygen]-the 2-(methyl mercapto) acetamide, the bromo-8-methyl of 2-[(3--6-quinolyl) oxygen]-N-(1, 1-dimethyl-2-propine-1-yl)-2-(methyl mercapto) acetamide and the bromo-6-quinolyl of 2-[(3-) oxygen]-N-(1, the 1-dimethyl ethyl) butyramide.
" fungicide, described fungicide is not the fungicide of component (a) and component (b1) to (b45); (b46) " also comprise (b46.6) N'-[4-[[3-[(4-chlorphenyl) methyl]-1; 2; 4-thiadiazoles-5-yl] oxygen]-2, the 5-3,5-dimethylphenyl]-N-ethyl-N-methyl azomethine acid amides, it it is believed that the C24-methyltransferase that the biosynthesis of inhibition sterols relates to.
In comprising following those embodiments of the invention, unless definition in addition in an embodiment, relevant to formula 1 its N-oxide and the salt that comprises, and except as otherwise noted, the comprise substituting group that in summary of the invention limit relevant to " compound of formula 1 " defines.
Embodiment 1: comprise the component (a) and the composition (b) that are described in summary of the invention, wherein, in formula 1, X is CHOH or NH.
Embodiment 2: the composition of embodiment 1, wherein X is CHOH.
Embodiment 3: the composition of embodiment 1, wherein X is NH.
Embodiment 4: comprise the component (a) and the composition (b) that are described in any one in summary of the invention or embodiment 1 to 3, and wherein in formula 1, R 1for halogen.
Embodiment 5: the composition of embodiment 4, wherein R 1for F, Cl or Br.
Embodiment 6: the composition of embodiment 5, wherein R 1for Cl or Br.
Embodiment 7: comprise the component (a) and the composition (b) that are described in any one in summary of the invention or embodiment 1 to 6, and wherein in formula 1, R 2for H, cyano group, F, Cl, Br or C 1-C 2alkoxyl.
Embodiment 8: the composition of embodiment 7, wherein R 2for H, cyano group, F, Cl, Br or methoxyl group.
Embodiment 9: the composition of embodiment 8, wherein R 2for cyano group, F, Cl or methoxyl group.
Embodiment 10: the composition of embodiment 9, wherein R 2for F or Cl.
Embodiment 11: the composition of embodiment 8, wherein R 2for H.
Embodiment 12: comprise the component (a) and the composition (b) that are described in any one in summary of the invention or embodiment 1 to 11, and wherein in formula 1, R 3for H or halogen.
Embodiment 13: the composition of embodiment 12, wherein R 3for H, F, Cl or Br.
Embodiment 14: the composition of embodiment 13, wherein R 3for H, F or Cl.
Embodiment 15: the composition of embodiment 14, wherein R 3for H or F.
Embodiment 16: comprise the component (a) and the composition (b) that are described in any one in summary of the invention or embodiment 1 to 11, and wherein in formula 1, R 3for halogen or methyl.
Embodiment 17: the composition of embodiment 16, wherein R 3for halogen.
Embodiment 18: the composition of embodiment 17, wherein R 3for F, Cl or Br.
Embodiment 19: embodiment 14 or 18 composition, wherein R 3for F or Cl.
Embodiment 20: embodiment 15 or 19 composition, wherein R 3for F.
Embodiment 21: comprise the component (a) and the composition (b) that are described in any one in summary of the invention or embodiment 1 to 20, and wherein in formula 1, R 4for F, Cl or Br.
Embodiment 22: the composition of embodiment 21, wherein R 4for Cl or Br.
Embodiment 23: comprise the component (a) and the composition (b) that are described in any one in summary of the invention or embodiment 1 to 22, and wherein in formula 1, R 5for H, cyano group, F, Cl, Br or C 1-C 2alkoxyl.
Embodiment 24: the composition of embodiment 23, wherein R 5for H, cyano group, F, Cl or methoxyl group.
Embodiment 25: the composition of embodiment 24, wherein R 5for cyano group, F, Cl or methoxyl group.
Embodiment 26: the composition of embodiment 25, wherein R 5for cyano group or F.
Embodiment 27: the composition of embodiment 26, wherein R 5for cyano group.
Embodiment 28: the composition of embodiment 26, wherein R 5for F.
Embodiment 29: comprise the component (a) and the composition (b) that are described in any one in summary of the invention or embodiment 1 to 28, and wherein in formula 1, R 6for H, F, Cl or Br.
Embodiment 30: the composition of embodiment 29, wherein R 6for H or F.
Embodiment 31: the composition of embodiment 30, wherein R 6for H.
Embodiment 32: comprise the component (a) and the composition (b) that are described in any one in summary of the invention or embodiment 1 to 31, and wherein in formula 1, R at most only 2and R 3in one be H(, R only 2and R 3in one be H, or R 2and R 3not all H).
Embodiment 33: the composition of embodiment 32, wherein R 3for H(and R 2not H).
Embodiment 34: the composition of embodiment 32, wherein R 2for H(and R 3not H).
Embodiment 35: the composition of embodiment 32, wherein R 2and R 3not all H.
Embodiment 36: comprise the component (a) and the composition (b) that are described in any one in summary of the invention or embodiment 1 to 35, and wherein in formula 1, R at most only 5and R 6for H(, R only 5and R 6in one be H, or R 5and R 6not all H).
Embodiment 37: the composition of embodiment 36, wherein R 6for H(and R 5not H).
Embodiment 38: the composition of embodiment 36, wherein R 5for H(and R 6not H).
Embodiment 39: the composition of embodiment 36, wherein R 5and R 6not all H.
Embodiment 40: comprise the component (a) and the composition (b) that are described in any one in summary of the invention or embodiment 1 to 39, and wherein in formula 1, R at most only 2, R 3, R 4and R 6in both be H.
Embodiment 41: the composition of embodiment 40, wherein R 2, R 3, R 4and R 6in both be H.
Embodiment 42: the composition of embodiment 40, wherein R at most only 2, R 3, R 4and R 6in one be H.
Embodiment 43: the composition of embodiment 42, wherein R 2, R 3, R 4and R 6in one be H.
Embodiment 44: comprise the component (a) and the composition (b) that are described in any one in summary of the invention or embodiment 1 to 43, wherein component (a) does not comprise the N-oxide of formula 1 compound.
Embodiment 45: comprise the component (a) and the composition (b) that are described in any one in summary of the invention or embodiment 1 to 44, wherein component (a) comprises and is selected from following compound:
N, two (the chloro-4-fluorophenyls of 2-)-1 of 4-, 3-dimethyl-1H-pyrazoles-5-amine (compound 47),
N-(2-is bromo-4, the 6-difluorophenyl)-4-(2, the 4-difluorophenyl)-1,3-dimethyl-1H-pyrazoles-5-amine (compound 143),
N-(2-is bromo-4, the 6-difluorophenyl)-the bromo-4-fluorophenyl of 4-(2-)-1,3-dimethyl-1H-pyrazoles-5-amine (compound 195),
N-(2-is bromo-4, the 6-difluorophenyl)-the chloro-4-fluorophenyl of 4-(2-)-1,3-dimethyl-1H-pyrazoles-5-amine (compound 144),
N-(4-chloro-2,6-difluoro phenyl) the chloro-4-fluorophenyl of-4-(2-)-1,3-dimethyl-1H-pyrazoles-5-amine (compound 81),
The chloro-2-fluorophenyl of 4-[5-[(4-) amino]-1,3-dimethyl-1H-pyrazoles-4-yl]-3,5-difluorophenyl formonitrile HCN (compound 40),
N-(2-is chloro-4, the 6-difluorophenyl)-the chloro-4-fluorophenyl of 4-(2-)-1,3-dimethyl-1H-pyrazoles-5-amine (compound 82),
4-[5-[(2-is chloro-4, the 6-difluorophenyl) amino]-1,3-dimethyl-1H-pyrazoles-4-yl]-3-fluorophenyl formonitrile HCN (compound 238),
The chloro-4-fluorophenyl of 4-[[4-(2-)-1,3-dimethyl-1H-pyrazoles-5-yl] oxygen]-3,5-difluorophenyl formonitrile HCN (compound 13),
The chloro-4-fluorophenyl of 4-(2-)-N-(2, the chloro-6-fluorophenyl of 4-bis-)-1,3-dimethyl-1H-pyrazoles-5-amine (compound 136),
The chloro-4-fluorophenyl of 4-(2-)-N-(2, the fluoro-4-anisyl of 6-bis-)-1,3-dimethyl-1H-pyrazoles-5-amine (compound 3),
The chloro-4-fluorophenyl of 4-(2-)-α-(2,4-difluorophenyl)-1,3-dimethyl-1H-pyrazoles-5-methyl alcohol (compound 122),
N-(2, the chloro-6-fluorophenyl of 4-bis-)-4-(2, the 4-difluorophenyl)-1,3-dimethyl-1H-pyrazoles-5-amine (compound 161),
4-(2, the 4-dichlorophenyl)-N-(2, the 4-difluorophenyl)-1,3-dimethyl-1H-pyrazoles-5-amine (compound 17),
4-(2, the fluoro-4-anisyl of 6-bis-)-1,3-dimethyl-N-(2,4,6-trifluorophenyl)-1H-pyrazoles-5-amine (compound 7),
4-[[1,3-dimethyl-4-(2,4,6-trifluorophenyl)-1H-pyrazoles-5-yl] oxygen]-3,5-difluorobenzonitrile (compound 8),
The chloro-4-fluorophenyl of 4-(2-)-chloro-6-fluorophenyl of N-(2-)-1,3-dimethyl-1H-pyrazoles-5-amine (compound 239),
The bromo-4-fluorophenyl of 4-(2-)-chloro-6-fluorophenyl of N-(2-)-1,3-dimethyl-1H-pyrazoles-5 amine (compound 240),
The bromo-6-fluorophenyl of N-(2-)-chloro-4-fluorophenyl of 4-(2-)-1,3-dimethyl-1H-pyrazoles-5-amine (compound 241),
The bromo-4-fluorophenyl of 4-(2-)-bromo-6-fluorophenyl of N-(2-)-1,3-dimethyl-1H-pyrazoles-5-amine (compound 244),
The bromo-6-fluorophenyl of N-(2-)-4-(2, the 4-difluorophenyl)-1,3-dimethyl-1H-pyrazoles-5-amine (compound 245),
The bromo-6-fluorophenyl of N-(2-)-4-(2, the 6-difluorophenyl)-1,3-dimethyl-1H-pyrazoles-5-amine (compound 247),
The chloro-4-fluorophenyl of 4-(2-)-fluoro-6-aminomethyl phenyl of N-(2-)-1,3-dimethyl-1H-pyrazoles-5-amine (compound 252),
The chloro-4-fluorophenyl of 4-(2-)-chloro-6-aminomethyl phenyl of N-(2-)-1,3-dimethyl-1H-pyrazoles-5-amine (compound 253),
The bromo-6-aminomethyl phenyl of N-(2-)-chloro-4-fluorophenyl of 4-(2-)-1,3-dimethyl-1H-pyrazoles-5-amine (compound 254),
The chloro-6-aminomethyl phenyl of N-(2-)-fluoro-4-anisyl of 4-(2-)-1,3-dimethyl-1H-pyrazoles-5-amine (compound 257),
The bromo-6-aminomethyl phenyl of N-(2-)-fluoro-4-anisyl of 4-(2-)-1,3-dimethyl-1H-pyrazoles-5-amine (compound 258),
The fluoro-4-anisyl of 4-(2-)-fluoro-6-aminomethyl phenyl of N-(2-)-1,3-dimethyl-1H-pyrazoles-5-amine (compound 259),
The chloro-6-fluorophenyl of N-(2-)-fluoro-4-anisyl of 4-(2-)-1,3-dimethyl-1H-pyrazoles-5-amine (compound 260),
The bromo-6-fluorophenyl of N-(2-)-fluoro-4-anisyl of 4-(2-)-1,3-dimethyl-1H-pyrazoles-5-amine (compound 261),
The chloro-4-anisyl of 4-(2-)-chloro-6-aminomethyl phenyl of N-(2-)-1,3-dimethyl-1H-pyrazoles-5-amine (compound 262),
The bromo-6-aminomethyl phenyl of N-(2-)-chloro-4-anisyl of 4-(2-)-1,3-dimethyl-1H-pyrazoles-5-amine (compound 263),
The bromo-6-aminomethyl phenyl of N-(2-)-chloro-4-anisyl of 4-(2-)-1,3-dimethyl-1H-pyrazoles-5-amine (compound 264),
The bromo-6-aminomethyl phenyl of N-(2-)-4-(2, the 4-difluorophenyl)-1,3-dimethyl-1H-pyrazoles-5-amine (compound 265),
The bromo-4-fluorophenyl of 4-(2-)-bromo-6-aminomethyl phenyl of N-(2-)-1,3-dimethyl-1H-pyrazoles-5-amine (compound 266),
The bromo-4-fluorophenyl of 4-(2-)-fluoro-6-aminomethyl phenyl of N-(2-)-1,3-dimethyl-1H-pyrazoles-5-amine (compound 267),
4-(2, the 4-difluorophenyl)-the fluoro-6-aminomethyl phenyl of N-(2-)-1,3-dimethyl-1H-pyrazoles-5-amine (compound 268),
The chloro-6-aminomethyl phenyl of N-(2-)-4-(2, the 4-difluorophenyl)-1,3-dimethyl-1H-pyrazoles-5-amine (compound 269),
4-(2, the 4-difluorophenyl)-N-(2, the 6-3,5-dimethylphenyl)-1,3-dimethyl-1H-pyrazoles-5-amine (compound 270),
The chloro-4-fluorophenyl of 4-(2-)-N-(2, the 6-3,5-dimethylphenyl)-1,3-dimethyl-1H-pyrazoles-5-amine (compound 271),
The bromo-6-fluorophenyl of N-(2-)-chloro-4-anisyl of 4-(2-)-1,3-dimethyl-1H-pyrazoles-5-amine (compound 273),
The chloro-6-fluorophenyl of N-(2-)-4-(2,4-difluorophenyl)-1,3-dimethyl-1H-pyrazoles-5-amine (compound 275) and
The bromo-4-fluorophenyl of 4-(2-)-chloro-6-aminomethyl phenyl of N-(2-)-1,3-dimethyl-1H-pyrazoles-5-amine (compound 276).
(in this sense, the compound group is within the scope of parent embodiment).
Embodiment 46: the composition of embodiment 45, wherein component (a) comprises and is selected from following compound: compound 3,7,8,13,17,40,47,81,82,122,136,143,144,161,195,238,239,240 and 241.
Embodiment 47: the composition of embodiment 46, wherein component (a) comprises and is selected from following compound: compound 3,7,8,13,17,40,47,81,82,122,136,143,144,161,195 and 238.
Embodiment 48: the composition of embodiment 45, wherein component (a) comprises and is selected from following compound: compound 239,240,241,244,245,247,252,253,254,257,258,259,260,261,262,263,264,265,266,267,268,269,270,271,273,275 and 276.
Embodiment 49: the composition of embodiment 48, wherein component (a) comprises and is selected from following compound: compound 239,240 and 241.
Embodiment 50: the composition of embodiment 45, wherein component (a) comprises and is selected from following compound: compound 195 and compound 238.
Embodiment 51: comprise the component (a) and the composition (b) that are described in any one in summary of the invention or embodiment 1 to 50, precondition is, when component (a) when being selected from following compound and forming:
The chloro-4-fluorophenyl of 4-(2-)-1,3-dimethyl-N-(2,4,6-trifluorophenyl)-1H-pyrazoles-5-amine (compound 4),
4-(2, the fluoro-4-anisyl of 6-bis-)-N-(2, the 4-difluorophenyl)-1,3-dimethyl-1H-pyrazoles-5-amine (compound 6),
4-(2, the fluoro-4-anisyl of 6-bis-)-1,3-dimethyl-N-(2,4,6-trifluorophenyl)-1H-pyrazoles-5-amine (compound 7),
4-(2, the 4-difluorophenyl)-1,3-dimethyl-N-(2,4,6-trifluorophenyl)-1H-pyrazoles-5-amine (compound 11),
The chloro-4-fluorophenyl of 4-[[4-(2-)-1,3-dimethyl-1H-pyrazoles-5-yl] oxygen]-3,5-difluorobenzonitrile (compound 13),
4-[[4-(2, the 6-difluorophenyl)-1,3-dimethyl-1H-pyrazoles-5-yl] oxygen]-3-fluorobenzonitrile (compound 130),
The chloro-4-fluorophenyl of 4-(2-)-N-(2, the 6-difluorophenyl)-1,3-dimethyl-1H-pyrazoles-5-amine (compound 46),
The chloro-4-fluorophenyl of 4-[[4-(2-)-1,3-dimethyl-1H-pyrazoles-5-yl] oxygen]-3-fluorobenzonitrile (compound 33),
The chloro-4-[[4-(2 of 3-, the 6-difluorophenyl)-1,3-dimethyl-1H-pyrazoles-5-yl] oxygen] benzonitrile (compound 127),
The chloro-4-fluorophenyl of 4-(2-)-α-(2,4-difluorophenyl)-1,3-dimethyl-1H-pyrazoles-5-methyl alcohol (compound 122),
N, two (the chloro-4-fluorophenyls of 2-)-1 of 4-, 3-dimethyl-1H-pyrazoles-5-amine (compound 47),
The chloro-4-fluorophenyl of N-(2-)-chloro-6-fluorophenyl of 4-(2-)-1,3-dimethyl-1H-pyrazoles-5-amine (compound 58),
N-(2-is chloro-4, the 6-difluorophenyl)-4-(2, the 6-difluorophenyl)-1,3-dimethyl-1H-pyrazoles-5-amine (compound 86),
N-(2-is chloro-4, the 6-difluorophenyl)-4-(2, the 4-difluorophenyl)-1,3-dimethyl-1H-pyrazoles-5-amine (compound 117),
N-(4-chloro-2,6-difluoro phenyl)-4-(2, the 6-difluorophenyl)-1,3-dimethyl-1H-pyrazoles-5-amine (compound 121),
N-(4-chloro-2,6-difluoro phenyl)-4-(2, the 4-difluorophenyl)-1,3-dimethyl-1H-pyrazoles-5-amine (compound 126),
The chloro-4-fluorophenyl of the chloro-4-[[4-(2-of 3-)-1,3-dimethyl-1H-pyrazoles-5-yl] oxygen] benzonitrile (compound 37),
The chloro-4-fluorophenyl of 4-[[4-(2-)-1,3-dimethyl-1H-pyrazoles-5-yl] amino]-3,5-difluorobenzonitrile (compound 25),
The chloro-4-fluorophenyl of N-(2-)-4-(2, the fluoro-4-anisyl of 6-bis-)-1,3-dimethyl-1H-pyrazoles-5-amine (compound 23),
α, two (the chloro-4-fluorophenyls of 2-)-1 of 4-, 3-dimethyl-1H-pyrazoles-5-methyl alcohol (compound 123),
N-(4-chloro-2,6-difluoro phenyl) the chloro-4-fluorophenyl of-4-(2-)-1,3-dimethyl-1H-pyrazoles-5-amine (compound 81),
N-(2-is chloro-4, the 6-difluorophenyl)-the chloro-4-fluorophenyl of 4-(2-)-1,3-dimethyl-1H-pyrazoles-5-amine (compound 82),
N-(2, the chloro-4-fluorophenyl of 6-bis-)-4-(2, the 4-difluorophenyl)-1,3-dimethyl-1H-pyrazoles-5-amine (compound 137),
The chloro-4-[5-[(2-of 3-is chloro-4, the 6-difluorophenyl) amino]-1,3-dimethyl-1H-pyrazoles-4-yl] benzonitrile (compound 108),
The chloro-4-[5-[(4-chloro-2,6-difluoro of 3-phenyl) amino]-1,3-dimethyl-1H-pyrazoles-4-yl] benzonitrile (compound 111),
The bromo-4-fluorophenyl of N-(2-)-4-(2, the 4-difluorophenyl)-1,3-dimethyl-1H-pyrazoles-5-amine (compound 118),
The chloro-4-fluorophenyl of 4-(2-)-N-(2, the chloro-6-fluorophenyl of 4-bis-)-1,3-dimethyl-1H-pyrazoles-5-amine (compound 136),
The chloro-4-fluorophenyl of 4-(2-)-N-(2, the chloro-4-fluorophenyl of 6-bis-)-1,3-dimethyl-1H-pyrazoles-5-amine (compound 138),
The bromo-4-fluorophenyl of 4-[[4-(2-)-1,3-dimethyl-1H-pyrazoles-5-yl] oxygen]-3-fluorobenzonitrile (compound 79),
The bromo-4-fluorophenyl of N-(2-)-chloro-4-fluorophenyl of 4-(2-)-1,3-dimethyl-1H-pyrazoles-5-amine (compound 73),
The bromo-4-fluorophenyl of 4-(2-)-1,3-dimethyl-N-(2,4,6-trifluorophenyl)-1H-pyrazoles-5-amine (compound 74),
N-(4-is bromo-2, the 6-difluorophenyl)-4-(2, the 4-difluorophenyl)-1,3-dimethyl-1H-pyrazoles-5-amine (compound 133),
The bromo-4-fluorophenyl of 4-[[4-(2-)-1,3-dimethyl-1H-pyrazoles-5-yl] oxygen]-3,5-difluorobenzonitrile (compound 65),
The bromo-4-fluorophenyl of 4-(2-)-N-(2-is chloro-4, the 6-difluorophenyl)-1,3-dimethyl-1H-pyrazoles-5-amine (compound 84),
The bromo-4-fluorophenyl of 4-(2-)-N-(4-chloro-2,6-difluoro phenyl)-1,3-dimethyl-1H-pyrazoles-5-amine (compound 129),
N-(4-is bromo-2, the 6-difluorophenyl)-the chloro-4-fluorophenyl of 4-(2-)-1,3-dimethyl-1H-pyrazoles-5-amine (compound 134),
The bromo-4-[[4-(2 of 3-, the 4-difluorophenyl)-1,3-dimethyl-1H-pyrazoles-5-yl] oxygen] benzonitrile (compound 139),
The chloro-4-[[4-(2 of 3-, the 4-difluorophenyl)-1,3-dimethyl-1H-pyrazoles-5-yl] oxygen] benzonitrile (compound 140),
N-(2, the chloro-6-fluorophenyl of 4-bis-)-4-(2, the 4-difluorophenyl)-1,3-dimethyl-1H-pyrazoles-5-amine (compound 141),
N-(2, the chloro-4-fluorophenyl of 6-bis-)-4-(2, the 6-difluorophenyl)-1,3-dimethyl-1H-pyrazoles-5-amine (compound 142),
N-(2-is bromo-4, the 6-difluorophenyl)-4-(2, the 4-difluorophenyl)-1,3-dimethyl-1H-pyrazoles-5-amine (compound 143),
N-(2-is bromo-4, the 6-difluorophenyl)-the chloro-4-fluorophenyl of 4-(2-)-1,3-dimethyl-1H-pyrazoles-5-amine (compound 144),
N-(4-is bromo-2, the 6-difluorophenyl)-4-(2, the 6-difluorophenyl)-1,3-dimethyl-1H-pyrazoles-5-amine (compound 145),
N-(2-is bromo-4, the 6-difluorophenyl)-4-(2, the 6-difluorophenyl)-1,3-dimethyl-1H-pyrazoles-5-amine (compound 146),
N-(2-is bromo-4, the 6-difluorophenyl)-the chloro-6-fluorophenyl of 4-(2-)-1,3-dimethyl-1H-pyrazoles-5-amine (compound 147),
α-chloro-4-fluorophenyl of (4-chloro-2,6-difluoro phenyl)-4-(2-)-1,3-dimethyl-1H-pyrazoles-5-methyl alcohol (compound 148),
4-[5-[(2-is chloro-4, the 6-difluorophenyl) amino]-1,3-dimethyl-1H-pyrazoles-4-yl]-3-fluorobenzonitrile (compound 238),
4-[5-[(4-chloro-2,6-difluoro phenyl) amino]-1,3-dimethyl-1H-pyrazoles-4-yl]-3-fluorobenzonitrile (compound 150),
α-(2-chloro-4,6-difluorophenyl)-chloro-4-fluorophenyl of 4-(2-)-1,3-dimethyl-1H-pyrazoles-5-methyl alcohol (compound 151),
α-(the bromo-4-fluorophenyl of 2-)-4-(2,4-difluorophenyl)-1,3-dimethyl-1H-pyrazoles-5-methyl alcohol (compound 152) and
α-(the bromo-4-fluorophenyl of 2-)-chloro-4-fluorophenyl of 4-(2-)-1,3-dimethyl-1H-pyrazoles-5-methyl alcohol (compound 153),
Component (b) comprises at least two kinds of Fungicidal compounds, and
(1) form when the binary combination of component (b) by two kinds of Fungicidal compounds, when wherein the one in Fungicidal compounds is Cyproconazole, Difenoconazole, epoxiconazole, metconazole, nitrile bacterium azoles, prothioconazoles or Tebuconazole, not to be that Fluoxastrobin, wide-spectrum bactericide, Boscalid, cyflufenamid, fluorine pyrrole bacterium acid amides, naphthalene pyrrole bacterium amine (isopyrazam), gram are received glad, metrafenone, pyrrole metsulfovax, ZEN 90160, the third oxygen quinoline, pyraclostrobin, fast promise are fragrant, encircle the third pyrrole bacterium amine (sedaxane) or oxime bacterium ester for another kind of Fungicidal compounds, and
(2) form when the triple combination of component (b) by three kinds of Fungicidal compounds, wherein a kind of in Fungicidal compounds is Cyproconazole, Difenoconazole, epoxiconazole, metconazole, nitrile bacterium azoles, prothioconazoles or Tebuconazole, and, when the another kind of Fungicidal compounds is ZEN 90160 or oxime bacterium ester, the 3rd antifungal compound is not the third oxygen quinoline.
Embodiments of the invention, comprise above embodiment 1-51 and any other embodiment as herein described, they can be combined in any way, and the description of modification not only is applicable to comprising the composition of formula 1 compound with at least one other Fungicidal compounds in an embodiment, and be applicable to comprising and there is the composition that at least one invertebrate pests is controlled formula 1 compound of compound or reagent, and the compound of applicable formula 1 and their composition, and be applicable to initial compounds and the midbody compound of preparation formula 1 compound.In addition, embodiments of the invention comprise above-described embodiment 1-51 and any other embodiment as herein described and their any combination that is applicable to method of the present invention.Therefore it should be noted that another embodiment is composition disclosed above, described composition comprises (a) at least one compound, and described compound is selected from compound, its N-oxide and salt thereof of formula mentioned above 1; Control compound or reagent with at least one invertebrate pests, precondition is, when when component (a), in being selected from embodiment 51, the compound of listed group forms, described composition comprises at least two kinds of invertebrate pests control compounds or reagent, or at least one additional Fungicidal compounds (i.e. Fungicidal compounds except formula 1 compound).
The combination of embodiment 1-51 can be illustrated by following:
Embodiment A 1: comprise the component (a) and the composition (b) that are described in summary of the invention, the compound or its salt that wherein component (a) comprises formula 1, wherein in formula 1,
R at most only 2and R 3in one be H; And
R at most only 5and R 6in one be H;
Embodiment A 2: the compound of embodiment A 1, wherein in formula 1,
R 1for F, Cl or Br;
R 2for H, cyano group, F, Cl, Br or methoxyl group;
R 3for H, F or Cl;
R 4for F, Cl or Br;
R 5for H, cyano group, F, Cl or methoxyl group; And
R 6for H or F.
Embodiment A 3: the compound of embodiment A 2, wherein in formula 1,
R 3for H or F; And
R 5for cyano group, F, Cl or methoxyl group.
Embodiment A 4: the composition of embodiment A 3, wherein component (a) comprises and is selected from following compound: compound 3, compound 7, compound 8, compound 13, compound 17, compound 40, compound 47, compound 81, compound 82, compound 122, compound 136, compound 143, compound 144, compound 161, compound 195, compound 238, compound 239, compound 240 and compound 241.
Embodiment A 5: the composition of embodiment A 4, wherein component (a) comprises and is selected from following compound: compound 3, compound 7, compound 8, compound 13, compound 17, compound 40, compound 47, compound 81, compound 82, compound 122, compound 136, compound 143, compound 144, compound 161, compound 195 and compound 238.
Embodiment A 6: comprise the component (a) and the composition (b) that are described in summary of the invention,
The compound or its salt that wherein component (a) comprises formula 1, wherein in formula 1,
X is NH;
R 1for halogen or methyl;
R 2for H;
R 3for halogen or methyl;
R 4for halogen;
R 5for H, cyano group, halogen or C 1-C 2alkoxyl; And
R 6for H or halogen;
Precondition is to work as R 1during for F, R 3for Cl, and work as R 1during for Cl, R 3for F.
Embodiment A 7: the compound of embodiment A 6, wherein in formula 1,
R 3for F or Cl.
Embodiment A 8: the compound of embodiment A 7, wherein in formula 1,
R 1for Cl or Br; And
R 3for F.
Embodiment A 9: the described composition of any one in embodiment A 6 to A8, wherein in formula 1, R at most only 5and R 6in one be H.
Embodiment A 10: the compound of embodiment A 9, wherein in formula 1,
R 4for F, Cl or Br;
R 5for H, cyano group, F, Cl or methoxyl group; And
R 6for H or F.
Embodiment A 11: the compound of embodiment A 10, wherein in formula 1,
R 5for cyano group, F, Cl or methoxyl group.
Embodiment A 12: the composition of embodiment A 6, wherein component (a) comprises and is selected from following compound: compound 239, compound 240 and compound 241.
Embodiment B 1: the composition described in summary of the invention (including but not limited to the composition of any one in embodiment 1 to 51 and A1 to A12), wherein component (b) comprises at least one compound, described compound is selected from (b1) benzimidazole methyl carbamate fungicide, as benomyl, carbendazim and thiophanate-methyl.
Embodiment B 2: the composition described in summary of the invention (including but not limited to the composition of any one in embodiment 1 to 51 and A1 to A12), wherein component (b) comprises at least one compound, described compound is selected from (b2) dicarboximide fungicide, as procymidone, iprodione and vinclozolin.
Embodiment B 3: the composition described in summary of the invention (including but not limited to the composition of any one in embodiment 1 to 51 and A1 to A12), wherein component (b) comprises at least one compound, described compound is selected from (b3) demethylation inhibitor fungicide, as epoxiconazole, Fluquinconazole, Triadimenol, simeconazoles, kind bacterium azoles, triforine, Cyproconazole, Difenoconazole, Flusilazole, Flutriafol, metconazole, nitrile bacterium azoles, prochloraz, propiconazole, prothioconazoles, Tebuconazole and fluorine ether azoles.
Embodiment B 4: the composition described in summary of the invention (including but not limited to the composition of any one in embodiment 1 to 51 and A1 to A12), wherein component (b) comprises at least one compound, described compound is selected from (b4) phenyl amide fungicide, as metalaxyl, metalaxyl, metalaxyl-M, M 9834, M 9834-M, furalaxyl, ofurace and Wakil.
Embodiment B 5: the composition described in summary of the invention (including but not limited to the composition of any one in embodiment 1 to 51 and A1 to A12), wherein component (b) comprises at least one compound, described compound is selected from (b5) amine/morpholine fungicide, as cartap, dodemorph, butadiene morpholine, tridemorph, Trimorfamid Fademorf, fenpropidin, pipron and volution bacterium amine.
Embodiment B 6: the composition described in summary of the invention (including but not limited to the composition of any one in embodiment 1 to 51 and A1 to A12), wherein component (b) comprises at least one compound, described compound is selected from (b6) phosphatide biosynthesis inhibitor fungicide, as edifenphos and Isoprothiolane.
Embodiment B 7: the composition described in summary of the invention (including but not limited to the composition of any one in embodiment 1 to 51 and A1 to A12), wherein component (b) comprises at least one compound, described compound is selected from (b7) carboxylic acid amides fungicide, as wide-spectrum bactericide, Boscalid, carboxin, naphthalene pyrrole bacterium amine (isopyrazam), the oxidation rust that withers
Spirit, penta benzene pyrrole bacterium amine (penflufen) and pyrrole metsulfovax.
Embodiment B 8: the composition described in summary of the invention (including but not limited to the composition of any one in embodiment 1 to 51 and A1 to A12), wherein component (b) comprises at least one compound, described compound is selected from (b8) hydroxyl (2-amino-) pyrimidine fungicide, phenol as phonetic as second.
Embodiment B 9: the composition described in summary of the invention (including but not limited to the composition of any one in embodiment 1 to 51 and A1 to A12), wherein component (b) comprises at least one compound, described compound is selected from (b9) aniline pyrimidine fungicide, as cyprodinil.
Embodiment B 10: the composition described in summary of the invention (including but not limited to the composition of any one in embodiment 1 to 51 and A1 to A12), wherein component (b) comprises at least one compound, described compound is selected from (b10) N-carbanilate fungicide, prestige as mould as second.
Embodiment B 11: the composition described in summary of the invention (including but not limited to the composition of any one in embodiment 1 to 51 and A1 to A12), wherein component (b) comprises at least one compound, described compound is selected from the outside inhibitor fungicide of (b11) quinone, as Fluoxastrobin, pyraclostrobin, azoles amine bacterium ester, gram receive glad, oxime bacterium ester, ZEN 90160, azoles bacterium ester, pyrrole bacterium benzene prestige (pyribencarb),
Figure BDA00002868169000301
cycloheximide triazole, Fenamidone, discostrobin, Enestroburin, dimoxystrobin, SSF 126, orysastrobin and fluoxastrobin.
Embodiment B 12: the composition described in summary of the invention (including but not limited to the composition of any one in embodiment 1 to 51 and A1 to A12), wherein component (b) comprises at least one compound, described compound is selected from (b12) phenylpyrrole fungicide compound, as fenpiclonil and fludioxonil.
Embodiment B 13: the composition described in summary of the invention (including but not limited to the composition of any one in embodiment 1 to 51 and A1 to A12), wherein component (b) comprises at least one compound, described compound is selected from (b13) quinoline fungicide, as fast promise sweet smell.
Embodiment B 14: the composition described in summary of the invention (including but not limited to the composition of any one in embodiment 1 to 51 and A1 to A12), wherein component (b) comprises at least one compound, described compound is selected from (b14) class lipid peroxidation inhibitor fungicide, as chloroneb.
Embodiment B 15: the composition described in summary of the invention (including but not limited to the composition of any one in embodiment 1 to 51 and A1 to A12), wherein component (b) comprises at least one compound, described compound is selected from (b15) melanocyte biosynthesis inhibitor-reductase fungicide, as pyroquilon and tricyclazole.
Embodiment B 16: the composition described in summary of the invention (including but not limited to the composition of any one in embodiment 1 to 51 and A1 to A12), wherein component (b) comprises at least one compound, described compound is selected from (b16) melanocyte biosynthesis inhibitor-dehydratase fungicide, as ring propionyl bacterium amine.
Embodiment B 17: the composition described in summary of the invention (including but not limited to the composition of any one in embodiment 1 to 51 and A1 to A12), wherein component (b) comprises at least one compound, described compound is selected from (b17) hydroxyanilines fungicide, as fenhexamid.
Embodiment B 18: the composition described in summary of the invention (including but not limited to the composition of any one in embodiment 1 to 51 and A1 to A12), wherein component (b) comprises at least one compound, described compound is selected from (b18) squalene-inhibitors of cyclooxygenases fungicide, as pyributicarb.
Embodiment B 19: the composition described in summary of the invention (including but not limited to the composition of any one in embodiment 1 to 51 and A1 to A12), wherein component (b) comprises at least one compound, described compound is selected from (b19) polyoxin fungicide, as polyoxin.
Embodiment B 20: the composition described in summary of the invention (including but not limited to the composition of any one in embodiment 1 to 51 and A1 to A12), wherein component (b) comprises at least one compound, described compound is selected from (b20) phenylurea fungicide, as Pencycuron.
Embodiment B 21: the composition described in summary of the invention (including but not limited to the composition of any one in embodiment 1 to 51 and A1 to A12), wherein component (b) comprises at least one compound, described compound is selected from the inner inhibitor fungicide of (b21) quinone, as the match seat goes out and amisulbrom.
Embodiment B 22: the composition described in summary of the invention (including but not limited to the composition of any one in embodiment 1 to 51 and A1 to A12), wherein component (b) comprises at least one compound, described compound is selected from (b22) benzamide fungicide, as oxamides.
Embodiment B 23: the composition described in summary of the invention (including but not limited to the composition of any one in embodiment 1 to 51 and A1 to A12), wherein component (b) comprises at least one compound, described compound is selected from (b23) enol pyranose aldehydic acid antibiotic fungicide, as blasticidin S-S.
Embodiment B 24: the composition described in summary of the invention (including but not limited to the composition of any one in embodiment 1 to 51 and A1 to A12), wherein component (b) comprises at least one compound, described compound is selected from (b24) own pyrans glycosyl antibiotic fungicide, as kasugarnycin.
Embodiment B 25: the composition described in summary of the invention (including but not limited to the composition of any one in embodiment 1 to 51 and A1 to A12), wherein component (b) comprises at least one compound, described compound is selected from (b25) glycopyranosyl antibiotic: the protein synthesis of antifungal agents, and as streptomycin.
Embodiment B 26: the composition described in summary of the invention (including but not limited to the composition of any one in embodiment 1 to 51 and A1 to A12), wherein component (b) comprises at least one compound, described compound is selected from (b26) glycopyranosyl antibiotic: trehalase and inositol biosynthesis fungicide, and as jinggangmeisu.
Embodiment B 27: the composition described in summary of the invention (including but not limited to embodiment 1 to 51 and the A1 composition to middle any one), wherein component (b) comprises at least one compound, described compound is selected from A12(b27) cyanoacetamide oxime fungicide, as white urea cyanogen.
Embodiment B 28: the composition described in summary of the invention (including but not limited to the composition of any one in embodiment 1 to 51 and A1 to A12), wherein component (b) comprises at least one compound, described compound is selected from (b28) carbamate fungicide, as Propamocarb, prothiocarb and iodo propinyl butyl carbamate.
Embodiment B 29: the composition described in summary of the invention (including but not limited to the composition of any one in embodiment 1 to 51 and A1 to A12), wherein component (b) comprises at least one compound, described compound is selected from the even fungicide of (b29) oxidative phosphorylation solution, as fluazinam, binapacryl, ferimzone, dinocap and karathane.
Embodiment B 30: the composition described in summary of the invention (including but not limited to the composition of any one in embodiment 1 to 51 and A1 to A12), wherein component (b) comprises at least one compound, described compound is selected from (b30) organotin fungicide, as fentin acetate.
Embodiment B 31: the composition described in summary of the invention (including but not limited to the composition of any one in embodiment 1 to 51 and A1 to A12), wherein component (b) comprises at least one compound, and described compound is selected from (b31) carboxylic acid fungicide, as
Figure BDA00002868169000321
quinoline acid.
Embodiment B 32: the composition described in summary of the invention (including but not limited to the composition of any one in embodiment 1 to 51 and A1 to A12), wherein component (b) comprises at least one compound, described compound is selected from (b32) heteroaromatic fungicide, as dislikes mould spirit.
Embodiment B 33: the composition described in summary of the invention (including but not limited to embodiment 1 to 51 and the A1 composition to middle any one), wherein component (b) comprises at least one compound, described compound is selected from A12(b33) phosphonate ester fungicide, as phosphorous acid and various salt thereof, comprise phosethyl-Al.
Embodiment B 34: the composition described in summary of the invention (including but not limited to the composition of any one in embodiment 1 to 51 and A1 to A12), wherein component (b) comprises at least one compound, described compound is selected from (b34) phthalamidic acid fungicide, as tecloftalam.
Embodiment B 51: the composition described in summary of the invention (including but not limited to the composition of any one in embodiment 1 to 51 and A1 to A12), wherein component (b) comprises at least one compound, described compound is selected from (b35) phentriazine fungicide, as azoles bacterium piperazine.
Embodiment B 36: the composition described in summary of the invention (including but not limited to the composition of any one in embodiment 1 to 51 and A1 to A12), wherein component (b) comprises at least one compound, described compound is selected from (b36) benzene-sulfonamide fungicide, as flusulfamide.
Embodiment B 37: the composition described in summary of the invention (including but not limited to the composition of any one in embodiment 1 to 51 and A1 to A12), wherein component (b) comprises at least one compound, described compound is selected from (b37) pyridazinone fungicide, as diclomezine.
Embodiment B 38: the composition described in summary of the invention (including but not limited to the composition of any one in embodiment 1 to 51 and A1 to A12), wherein component (b) comprises at least one compound, described compound is selected from (b38) thiophene-carboxylic acid amides fungicide, as Silthiopham.
Embodiment B 39: the composition described in summary of the invention (including but not limited to the composition of any one in embodiment 1 to 51 and A1 to A12), wherein component (b) comprises at least one compound, described compound is selected from (b39) pyrimidine acid amides fungicide, as the difluoro woods.
Embodiment B 40: the composition described in summary of the invention (including but not limited to the composition of any one in embodiment 1 to 51 and A1 to A12), wherein component (b) comprises at least one compound, described compound is selected from (b40) carboxylic acid amide fungicide, as dimethomorph, benzene metsulfovax, cumene metsulfovax, Propineb, downy mildew go out, mandipropamid and flumorph.
Embodiment B 41: the composition described in summary of the invention (including but not limited to the composition of any one in embodiment 1 to 51 and A1 to A12), wherein component (b) comprises at least one compound, described compound is selected from (b41) tetracycline antibiotic fungicide, as oxytetracycline.
Embodiment B 42: the composition described in summary of the invention (including but not limited to the composition of any one in embodiment 1 to 51 and A1 to A12), wherein component (b) comprises at least one compound, described compound is selected from (b42) thiocarbamate fungicide, as methasulfocarb.
Embodiment B 43: the composition described in summary of the invention (including but not limited to the composition of any one in embodiment 1 to 51 and A1 to A12), wherein component (b) comprises at least one compound, described compound is selected from (b43) benzamide fungicide, as fluopicolide and fluorine pyrrole bacterium acid amides.
Embodiment B 44: the composition described in summary of the invention (including but not limited to the composition of any one in embodiment 1 to 51 and A1 to A12), wherein component (b) comprises at least one compound, described compound is selected from (b44) host plant defence induction type fungicide, as my acid benzene-S-methyl.
Embodiment B 45: the composition described in summary of the invention (including but not limited to the composition of any one in embodiment 1 to 51 and A1 to A12), wherein component (b) comprises at least one compound, described compound is selected from (b45) multidigit point-contact type fungicide, as Cupravit, copper sulphate, Kocide SD, bordeaux mixture composition (ternary copper sulphate), elementary sulfur, mancozeb, Carbatene, Propineb, ferbam, maneb, arasan, zineb, ziram, folpet, captan, difoltan and tpn.
Embodiment B 46: the composition described in summary of the invention (including but not limited to the composition of any one in embodiment 1 to 51 and A1 to A12), wherein component (b) comprises the compound that at least one is selected from (b46) fungicide, described fungicide is not the fungicide of component (a) and component (b1) to (b45), as Guardian, cyflufenamid, the third oxygen quinoline, metrafenone, methoxy benzene pyridine bacterium (pyriofenone), hot azoles mepanipyrim (ametoctradin), diclomezin, Neo-Asozin, amine benzene pyrrole bacterium ketone, pyrrolnitrin, chinomethionat, isobutyl ethoxyquin (tebufloquin), the chloro-6-(2 of 5-, 4, the 6-trifluorophenyl)-7-(4-methyl piperidine-1-yl) [1, 2, 4] triazol [1, 5-a] pyrimidine (BAS600), the iodo-3-propyl group of 2-butoxy-6--4H-1-benzopyran-4-one, the 3-[5-(4-chlorphenyl)-2, 3-dimethyl-3-is different azoles quinoline base] pyridine (SYP-Z048), the N-[1-[[[1-(4-cyano-phenyl) ethyl] sulfonyl] methyl] propyl group] carbamic acid-4-fluorobenzene ester (XR-539), the N-[[(cyclo propyl methoxy) amino] [the 6-(difluoro-methoxy)-2, the 3-difluorophenyl] methylene] phenyl acetamide, the chloro-3-(trifluoromethyl of N'-[4-[4-) phenoxy group]-2, the 5-3,5-dimethylphenyl]-N-ethyl-N-methyl azomethine acid amides, the fluoro-5-(trifluoromethyl of 2-[[2-) phenyl] sulphur]-the 2-[3-(2-anisyl)-the inferior thiazolidinyl of 2-] acetonitrile (OK-5203), the chloro-2-nitrobenzophenone of N-(4-)-N-ethyl-4-methyl benzenesulfonamide (TF-991) and 1-[(2-propylene sulfenyl) carbonyl]-the 2-(1-Methylethyl)-the 4-(2-aminomethyl phenyl)-5-amino-1H-pyrazoles-3-ketone.
Embodiment B 47: the composition described in summary of the invention (including but not limited to the composition of any one in embodiment 1 to 51 and A1 to A12), wherein component (b) comprises at least one and is selected from following Fungicidal compounds (fungicide): Fluoxastrobin, gram is received glad, oxime bacterium ester, pyraclostrobin, azoles bacterium ester, azoles amine bacterium ester, ZEN 90160, dimoxystrobin, SSF 126/SSF 126, carbendazim, tpn, fast promise sweet smell, metrafenone, methoxy benzene pyridine bacterium (pyriofenone), cyflufenamid, fenpropidin, butadiene morpholine, bromuconazole, Cyproconazole, Difenoconazole, epoxiconazole, RH-7592, Flusilazole, own azoles alcohol, plant the bacterium azoles, metconazole, nitrile bacterium azoles, penconazole, propiconazole, the third oxygen quinoline, prothioconazoles, Tebuconazole, triticonazole,
Figure BDA00002868169000352
cycloheximide triazole, prochloraz, pyrrole metsulfovax and Boscalid (Boscalid).
Embodiment B 48: the composition of Embodiment B 47, wherein component (b) comprises at least one and is selected from following compound: Fluoxastrobin, gram receive glad, oxime bacterium ester, pyraclostrobin, azoles amine bacterium ester, azoles bacterium ester, ZEN 90160, dimoxystrobin, SSF 126/SSF 126, fast promise sweet smell, metrafenone, methoxy benzene pyridine bacterium (pyriofenone), cyflufenamid, fenpropidin, butadiene morpholine, Cyproconazole, Difenoconazole, epoxiconazole, Flusilazole, metconazole, nitrile bacterium azoles, propiconazole, the third oxygen quinoline, prothioconazoles, Tebuconazole, triticonazole,
Figure BDA00002868169000353
cycloheximide triazole and pyrrole metsulfovax.
Embodiment B 49: the composition described in summary of the invention (including but not limited to the composition of any one in embodiment 1 to 51 and A1 to A12), wherein component (b) comprises at least one Fungicidal compounds, described Fungicidal compounds is selected from formula A1 compound and salt thereof, and its Chinese style A1 and substituting group thereon are as disclosed for the 6-quinolyl oxygen yl acetamide compound of (b46.5) class as this paper.
Embodiment B 50: the composition of Embodiment B 49, wherein component (b) comprises at least one and is selected from the bromo-6-quinolyl of following Fungicidal compounds: 2-[(3-) oxygen]-N-(1, 1-dimethyl-2-butine-1-yl)-2-(methyl mercapto) acetamide, 2-[(3-acetenyl-6-quinolyl) oxygen]-the N-[1-(methylol)-1-methyl-2-propine-1-yl]-the 2-(methyl mercapto) acetamide, N-(1, 1-dimethyl-2-butine-1-yl)-2-[(3-acetenyl-6-quinolyl) oxygen]-the 2-(methyl mercapto) acetamide, the bromo-8-methyl of 2-[(3--6-quinolyl) oxygen]-N-(1, 1-dimethyl-2-propine-1-yl)-2-(methyl mercapto) acetamide and the bromo-6-quinolyl of 2-[(3-) oxygen]-N-(1, the 1-dimethyl ethyl) butyramide.
It should be noted that the composition of any one in embodiment as herein described, comprise embodiment 1 to 51, A1 to A12 and B1 to B50, relevant to formula 1 its salt that comprises wherein, but do not comprise its N-oxide; Therefore, phrase " compound of formula 1 " can be replaced by phrase " compound or its salt of formula 1 ".At the said composition Notable, the compound or its salt that component (a) comprises formula 1.
Also noteworthy is that Fungicidal composition of the present invention as embodiment, embodiment 1 to 51, the A1 to A12 that described composition comprises the antifungal effective dose and the composition of B1 to B50, and at least one annexing ingredient, described annexing ingredient is selected from surfactant, solid diluent and liquid diluent.
Embodiments of the invention also comprise for controlling the method for the plant disease caused by plant pathogenic fungi, and described method comprises to plant or its part or uses the composition (for example, as comprising the composition of preparation composition as described herein) of any one in embodiment 1 to 51, the A1 to A12 of antifungal effective dose and B1 to B50 to plant seed or rice shoot.Embodiments of the invention also comprise the method for the disease that protective plant or plant seed are avoided being caused by fungal pathogens, and described method comprises the composition of using any one in embodiment 1 to 51, the A1 to A12 of antifungal effective dose and B1 to B50 to plant or plant seed.
Some embodiments of the present invention relate to the plant disease of controlling main torment leaves of plants or prevent plant disease and/or use composition of the present invention (that is, plant rather than seed) to leaves of plants.Preferred using method comprises those that relate to above-mentioned preferred composition; And the disease with special-effect is controlled and is comprised the plant disease caused by fungal plant pathogen.Can be conducive to control disease and delaying drug resistance development for fungicide combination of the present invention.
Embodiment of the method also comprises:
Embodiment C 1: protective plant is avoided the method for disease; described disease is selected from powdery mildew, rust tick and Septoria disease; described method comprises composition from the antifungal effective dose to plant that use, and described composition comprises the component (a) that is described in any one in summary of the invention or embodiment 1 to 51 and (b).
Embodiment C 2: the method for Embodiment C 1, wherein disease is the powdery mildew disease, and the component of composition (b) comprises at least one Fungicidal compounds, described Fungicidal compounds is selected from outside inhibitor (QoI) fungicide of (b4) demethylation inhibitor (DMI) fungicide, (b11) quinine and (b46.4) the third oxygen quinoline.
Embodiment C 3: the method for Embodiment C 2, wherein disease is wheat powdery mildew.
Embodiment C 4: the method for Embodiment C 2 or C3, wherein component (b) comprises the Fungicidal compounds that at least one is selected from (b4) DMI fungicide.
Embodiment C 5: the method for Embodiment C 4, wherein component (b) comprises at least one and is selected from following Fungicidal compounds: Cyproconazole, Difenoconazole, epoxiconazole, nitrile bacterium azoles, prothioconazoles and fluorine ether azoles.
Embodiment C 6: the method for Embodiment C 5, wherein component (b) comprises at least one and is selected from following Fungicidal compounds: Cyproconazole, Difenoconazole and prothioconazoles.
Embodiment C 7: the method for Embodiment C 2 or C3, wherein component (b) comprises the Fungicidal compounds that at least one is selected from (b11) QoI fungicide.
Embodiment C 8: the method for Embodiment C 7, wherein component (b) comprises at least one and is selected from following Fungicidal compounds: Fluoxastrobin, ZEN 90160 and pyraclostrobin.
Embodiment C 9: the method for Embodiment C 2 or C3, wherein component (b) comprises (b46.4) third oxygen quinoline.
Embodiment C 10: the method for Embodiment C 1, wherein disease is rust ixodism evil, and the component of composition (b) comprises butadiene morpholine.
Embodiment C 11: the method for Embodiment C 10, wherein disease is the wheat leaf rust tick.
Embodiment C 12: the method for Embodiment C 1, wherein disease is the Septoria disease, and the component of composition (b) comprises at least one and is selected from following Fungicidal compounds: epoxiconazole, metalaxyl (comprising metalaxyl-M), Propineb and butadiene morpholine.
Embodiment C 13: the method for Embodiment C 12, wherein disease is wheat leaf rash spot.
Embodiment C 14: protective plant is avoided the method for Septoria disease, and described method comprises to plant uses the Embodiment B 49 of antifungal effective dose or the composition of B50.
Embodiment C 15: the method for Embodiment C 14, wherein the disease lipoxygenase causes.
Embodiment C 16: the method for Embodiment C 14 or C15, wherein disease is wheat leaf rash spot.
Embodiment C 17: the method for any one in Embodiment C 1 to C16, wherein component (a) and (b) use with the effective dose of working in coordination with (and with collaborative ratio) relative to each other.
It should be noted that the embodiment corresponding to Embodiment C 1 to C17 of the method about controlling the plant disease caused by fungal plant pathogen, described method comprises the Fungicidal composition of the present invention of using the antifungal effective dose to plant or its part.
As mentioned in summary of the invention, the invention still further relates to compound or its N-oxide or its salt of formula 1.What also mentioned is embodiments of the invention, comprises embodiment 1-51, also relates to the compound of formula 1.Therefore, the combination of embodiment 1-51 is also illustrated by following:
Embodiment D1: the compound of formula 1 or its N-oxide or its salt, wherein
X is NH;
R 1for halogen or methyl;
R 2for H;
R 3for halogen or methyl;
R 4for halogen;
R 5for H, cyano group, halogen or C 1-C 2alkoxyl; And
R 6for H or halogen;
Precondition is to work as R 1during for F, R 3for Cl, and work as R 1during for Cl, R 3for F.
Embodiment D2: the compound in embodiment D1, wherein
R 3for F or Cl.
Embodiment D3: the compound in embodiment D2, wherein
R 1for Cl or Br; And
R 3for F.
Embodiment D4: the compound of any one in embodiment D1 to D4, wherein R at most only 5and R 6in one be H.
Embodiment D5: the compound in embodiment D4, wherein
R 4for F, Cl or Br;
R 5for H, cyano group, F, Cl or methoxyl group; And
R 6for H or F.
Embodiment D6: the compound in embodiment D5, wherein
R 5for cyano group, F, Cl or methoxyl group.
Embodiment D7: the compound of any one in embodiment D1 to D6, wherein compound is not the form form of formula 1 or its salt (that is, for) of N-oxide.
Embodiment D8: the compound of embodiment D1, described compound is selected from:
The chloro-4-fluorophenyl of 4-(2-)-chloro-6-fluorophenyl of N-(2-)-1,3-dimethyl-1H-pyrazoles-5-amine (compound 239),
The bromo-4-fluorophenyl of 4-(2-)-chloro-6-fluorophenyl of N-(2-)-1,3-dimethyl-1H-pyrazoles-5 amine (compound 240) and
The bromo-6-fluorophenyl of N-(2-)-chloro-4-fluorophenyl of 4-(2-)-1,3-dimethyl-1H-pyrazoles-5-amine (compound 241).
Additional embodiment comprises Fungicidal composition, and described composition comprises: the compound of any one in (1) embodiment D1 to D8; (2) at least one annexing ingredient, described annexing ingredient is selected from surfactant, solid diluent and liquid diluent.Additional embodiment also comprises the method for the disease that protective plant or plant seed are avoided being caused by fungal pathogens; described method comprises the compound (be applied directly on plant or plant seed, or for example, use by environment (somatomedin)) of using any one in the embodiment D1 to D8 of antifungal effective dose to plant (or its part) or plant seed.It should be noted that the embodiment of the method for controlling the plant disease caused by fungal plant pathogen, described method comprises the compound of using any one in the embodiment D1 to D8 of antifungal effective dose to plant or its part.
Can use one or more following methods described in scheme 1-17 and the compound of modification preparation formula 1.Except as otherwise noted, hereinafter in the compound of formula 1-26, R 1, R 2, R 3, R 4, R 5and R 6definition as defined at summary of the invention above.Formula 1a, 1b and 1c are each subset of formula 1; Formula 4a and 4b are each subset of formula 4; Formula 6a and 6b are each subset of formula 6; Formula 11a is the subset of formula 11; And formula 23a is the subset of formula 23.Except as otherwise noted, for the substituting group of each subset formula as defined for its parent formula.
As shown in scheme 1, the compound of the formula 1 that wherein X is NH can pass through the 1H-pyrazole compound of formula 2 and various methylating reagent (suc as formula 3), as iodomethane, methylmesylate (as methyl mesylate (OMs) or toluenesulfonic acid methyl esters (OTs)) or trimethyl phosphate, preferably at organic or inorganic alkali, as 1, in the situation that 8-diazabicylo [5.4.0] 11 carbon-7-alkene, potash or potassium hydroxide exist, and reaction preparation in the solvent such as DMF (DMF), oxolane (THF), toluene or water.
scheme 1
As shown in scheme 2, but the compound of the compound passing type 4 of formula 1 (the 5-amino-pyrazol that is NH for X, the 5-hydroxypyrazoles that is perhaps O for X (5-pyrazolone)) and comprise leaving group G(, halogen or (halogen) alkyl sulfonic ester) the aromatic compounds of formula 5, optionally in the situation that the metallic catalyst existence, and general in the situation that alkali and the reaction preparation existed such as the polar non-solute of DMF or dimethyl sulfoxide (DMSO).The direct substitution reaction of the compound of the formula 5 that for example, wherein phenyl ring comprises electron-withdrawing substituent by leaving group G from encircling is to provide the compound of formula 1.The method of scheme 2 illustrates by the step D of synthetic example 6.The commercially available acquisition of the compound of formula 5, or their preparation is known in the art.
scheme 2
Figure BDA00002868169000411
Method according to scheme 2, the compound that lacks the formula 5 of enough electron-withdrawing substituents for the compound of the formula 4 that wherein X is O or NH and aromatic ring wherein, perhaps, in order to improve reaction rate, yield or product purity, metallic catalyst (as metal or slaine) is used the reaction that can be conducive to expectation to excessive amount with catalytic amount.Usually for these conditions, G is Br or I or sulfonate, as OS(O) 2cF 3or OS(O) 2(CF2) 3cF 3.For example, can use the mantoquita compound (as CuI and N, the N'-dimethyl-ethylenediamine, proline or pyridine), palladium compound (as three (dibenzalacetone) two palladiums (0)) or palladium salt (as acid chloride) with such as 4, two (diphenylphosphino)-9 of 5-, 9-dimethyl oxa-anthracene (i.e. " Xantphos "), 2-dicyclohexyl phosphino--2', 4', 6'-tri isopropyl biphenyl (i.e. " Xphos ") or 2, two (diphenylphosphino)-1 of 2'-, the part of 1'-binaphthalene (i.e. " BINAP "), such as potash, cesium carbonate, in the situation that the alkali of benzene sodium oxide molybdena or uncle-sodium butoxide exists, such as N, dinethylformamide, 1, the 2-dimethoxy-ethane, dimethyl sulfoxide (DMSO), 1, in the solvent of 4-dioxane or toluene, optionally with the alcohol such as ethanol, mix.Alternatively, as in scheme 3 illustrated, the compound of formula 1a (formula 1 that wherein X is NH) but the compound (being 5-bromine pyrazoles or other pyrazoles replaced by leaving group on the 5-position) of passing type 6 with the compound of formula 7, be similar to above for the preparation of reacting under the condition of scheme 2 described those metal catalytics.The method of scheme 3 illustrates by the step C of synthetic example 1 and the step e of synthetic example 2.The commercially available acquisition of the compound of formula 7, or their preparation is known in the art.
scheme 3
Figure BDA00002868169000421
As shown in scheme 4, the compound of the formula 6 that wherein G is Br or I, but the 5-amino-pyrazol of passing type 4a (be formula 4, wherein X is NH), under the diazotising condition, is prepared with the mantoquita combination that comprises bromine or iodine under the existence of the mantoquita that comprises bromine or iodine or subsequently.For example,, at CuBr 2in situation about existing, in the solvent such as acetonitrile, to the 5-amino-pyrazol solution of formula 4a, add the tert-butyl nitrite so that the 5-bromine pyrazoles of corresponding formula 6 to be provided.Similarly, the 5-amino-pyrazol of formula 4a can be converted to diazol and then be transformed into the 5-halogen pyrazoles of corresponding formula 6, by with natrium nitrosum solvent as water, acetic acid or trifluoroacetic acid in, usually comprising identical halide atoms, (for G, be I, as the HI aqueous solution) process under the existence of inorganic acid, use subsequently corresponding copper (I) or copper (II) salt according to conventional method well-known to those having ordinary skill in the art is processed.The method of scheme 4 illustrates by the step B of synthetic example 1 and the step D of synthetic example 2.
scheme 4
Figure BDA00002868169000422
As shown in scheme 5, the 5-bromine pyrazoles of formula 6a (be formula 6, wherein G is Br) can be by the 5-hydroxypyrazoles by formula 4b (formula 4 that wherein X is O) and phosphorus tribromide, as at Tetrahedron Lett.2000,41(24), the reaction preparation described in 4713.
scheme 5
Figure BDA00002868169000431
As shown in scheme 6, the 5-hydroxypyrazoles of formula 4b also can be used to 5-fluoroalkyl sulfonyl (as 5-trifluoromethane sulfonyl group, the 5-nine fluorine butyl sulfonyls) pyrazoles (be formula 6, wherein G is the fluoroalkyl sulfonyl) of preparation formula 6b; as at Synlett; 2004, the 5th volume, described in 795 pages.
scheme 6
Figure BDA00002868169000432
As shown in scheme 7, the 4-bromine or iodine that the compound of formula 1 can be by the formula 10 that wherein X is O or NH reacts preparation for the organo-metallic compound of pyrazoles and formula 11 under transition metal-catalyzed cross-coupling reaction condition.The 4-bromine or iodine of formula 10, for the organomagnesium reagent of pyrazoles and boric acid, trialkyltin, zinc or formula 11, has suitable part (as triphenylphosphine (PPh 3), dibenzalacetone (dba), dicyclohexyl (2', 6'-dimethoxy [1,1'-biphenyl]-2-yl) phosphine (SPhos)) palladium or the compound that corresponding formula 1 is provided of the reaction in Raney nickel and alkali (if necessary) situation about existing.For example, wherein M is B(OH) 2, B(OC(CH 3) 2c(CH 3) 2o) or B
Figure BDA00002868169000442
li ⊕aryl boric acid or the derivative of replacement, suc as formula 11 with the 4-of formula 10 bromo-or 4-iodine pyrazoles in the situation that two (triphenylphosphine) palladium chloride (II) and existing such as the aqueous bases of sodium carbonate or potassium hydroxide, such as 1, the 4-dioxane, 1, the 2-dimethoxy-ethane, in the solvent of toluene or ethanol, react, or under anhydrous condition with such as the part of phosphine oxide or phosphite ligands (as diphenyl phosphine oxide) and potassium fluoride such as 1, in the solvent of 4-dioxane, reaction is (referring to Angewandte Chemie, international version 2008, 47(25), 4695-4698) so that the compound of corresponding formula 1 to be provided.The method of scheme 7 illustrates by the step C of this synthetic example 3.
scheme 7
Figure BDA00002868169000441
As in scheme 8 illustrated, the compound of formula 4a (formula 4 that wherein X is NH) can be by by the compound of the compound of formula 12 and formula 11a (suc as formula 11 compounds, wherein M be B(OH) 2) use as the preparation of the reaction for the described transition metal-catalyzed cross-coupling reaction condition of the method for scheme 7.
scheme 8
Figure BDA00002868169000451
As in scheme 9 illustrated, the pyrazoles that wherein X is O or NH and the G formula 10 that is Br or I is by the unsubstituted pyrazoles in 4-position (formula 13) and halide reagent, as bromine, sodium bromite, N-bromine succinimide (NBS) or N-iodine succinimide (NIS) at solvent as acetic acid, acetonitrile, N, dinethylformamide, N, N-dimethylacetylamide or 1, the mixture of 4-dioxane or water and above-mentioned solvent, easily prepare in environmental temperature to the reaction in the solvent boiling point temperature range.The method of scheme 9 illustrates by the step B of synthetic example 3.
scheme 9
As in scheme 10 illustrated, use and be similar to those reaction conditions for the method for scheme 9, the pyrazoles of the formula 14 that wherein X is NH can be transformed into intermediate 12, and it can be used for preparation as the compound at the formula 4a described in scheme 8.Can be prepared by methods known in the art by the compound of the formula that wherein X is NH.The commercially available acquisition of compound of the formula 14 that in addition, wherein X is NH.
scheme 10
Figure BDA00002868169000461
As shown in scheme 11, those steps that formula 13 compounds that wherein X is O or NH can be used by the method that is similar to scheme 2 are by the compound preparation of corresponding formula 14.The method of scheme 11 illustrates by the steps A of synthetic example 3.The commercially available acquisition of the compound of formula 14 or can be prepared by methods known in the art.
scheme 11
Figure BDA00002868169000462
As shown in scheme 12, the compound of formula 1b (formula 1 that wherein X is CHOH), can by with organometallic reagent (being formula 15) as lithium alkylide, preferred n-BuLi or alkyl magnesium reagent, preferably the compound of isopropylmagnesium chloride (optionally with the lithium chloride complexing) processing formula 6, pass through the benzaldehyde preparation of the replacement of adding type 16 subsequently.The method of scheme 12 illustrates by synthetic example 5.Alternatively, the compound of formula 1b can be by being used the ketone preparation of standard method well known in the art (as the sodium borohydride in methyl alcohol or methyl alcohol) reduction-type 1c.But the electric precursor reactant preparation of the same metal pyrazole derivatives of the compound of the ketone passing type 6 of formula 19 and the carbon of formula 17 or 18 parent.Reaction temperature can be at-90 ℃ to the reaction dissolvent boiling spread;-78 ℃ of temperature to environmental temperature are normally preferred, and when using alkyl lithium reagents, the temperature of-78 to-10 ℃ is preferred, and, owing to using alkyl magnesium reagent ,-20 ℃ is preferred to environmental temperature.Multi-solvents is useful, as toluene, ether, oxolane or dimethoxymethane; Anhydrous tetrahydro furan is preferred.The second metal component as zinc chloride, zinc bromide or cuprous salt, as cupric iodide (I) or copper cyanider (I), can advantageously add, in case the compound that the electric body of wherein said parent is formula 18 before the electric body of parent.Formula 16,17 and 18 the commercially available acquisition of carbonyl intermediates or can be prepared by methods known in the art.
scheme 12
Figure BDA00002868169000471
Be recognized that by those skilled in the art, be similar to those reactions shown in scheme 12 and also can use lack substituent pyrazoles on 4, therefore provide some to can be used for the compound of the formula 13 of the method summarized in scheme 9.
The usual method that can be used for the 5-amino-pyrazol of preparation formula 4a is known in this area; Referring to for example Journal f ü r Praktische Chemie(Leipzig) 1911,83,171 and J.Am.Chem.Soc.1954,76,501.These class methods are in scheme 13 illustrated.The method of scheme 13 illustrates by the steps A of this synthetic example 1 and the step C of this synthetic example 2.
scheme 13
Figure BDA00002868169000481
Similarly, the usual method that can be used for the 5-hydroxypyrazoles of preparation formula 4b is known in this area; Referring to for example Annalen der Chemie1924,436,88.These class methods are in scheme 14 illustrated.The method of scheme 14 illustrates by the step C of this synthetic example 6.
scheme 14
Figure BDA00002868169000482
As shown in scheme 15, the compound of formula 1a (formula 1 that wherein X is NH) can be according to conventional method known in the art condensation preparation in such as ethanol or methanol solvate by the compound of formula 23 and methyl hydrazine (formula 21), and optionally at acid or base catalyst, in the situation as acetic acid, piperidines or sodium methoxide existence.The method of scheme 15 illustrates by the step B of synthetic example 4 and the step C of synthetic example 7.
scheme 15
Figure BDA00002868169000491
Be similar to a certain extent the method for scheme 15, but prepared similarly by the compound of the compound passing type 2 of the formula 23 that wherein X is NH and hydrazine condensation.The method is described in Chemistry ofHeterocyclic Compounds,, 41(1 in 2005) volume, the 105-110 page.
As shown in scheme 16, the compound of formula 23 (R wherein 32for H or low alkyl group, as CH 3, CH 2cH 3or (CH 2) 2cH 3but) the ketenes two thio ketal ization compounds of passing type 24 correspondences and the compound of formula 7, optionally in the situation that exist such as the alkali of sodium hydride or ethylmagnesium chloride, in the solvent such as toluene, oxolane or dimethoxymethane, at-10 ℃ to the preparation of the reaction in the boiling temperature scope of described solvent.Referring to for example, J.Heterocycl.Chem.1975,12(1), 139.The method that can be used for the compound of preparation formula 24 is known in the art.
scheme 16
As shown in scheme 17, the compound of formula 23a (that is, the dynamic isomer of formula 23, wherein R 32for H) but the arylprop ketonic compound of the isothiocyanate compound of passing type 25 correspondences and formula 26 react preparation.Referring to for example Zhurnal Organicheskoi Khimii, nineteen eighty-two, 18(12) volume, the 2501st page.The alkali that can be used for this reaction comprises sodium hydride, alkoxide base (as potassium tert-butoxide or caustic alcohol), potassium hydroxide, sodium hydroxide, potash or amine alkali (as triethylamine or DIPEA).Available multi-solvents, as oxolane, ether, toluene, DMF, alcohol (as ethanol), ester (as ethyl acetate or isopropyl acetate) or their mixture.Select the solvent compatible with selected alkali, as known in the art.Reaction temperature can be at-78 ℃ to the solvent boiling point scope.A useful mixture of alkali and solvent is the potassium tert-butoxide in oxolane, under-70 to 0 ℃, the solution of the carbonyls of the isothiocyanates of adding type 25 and formula 26 wherein, they can be mixed into a kind of solution or add respectively, preferably add carbonyls, add subsequently isothiocyanates.The method of scheme 17 illustrates by the steps A of synthetic example 4 and the step C of synthetic example 7.
scheme 17
Figure BDA00002868169000501
The carbonyl thioamides of formula 23a also can be by making corresponding keto-amide and sulfuration reagent, as Lawesson reagent or P 2s 5the reaction preparation; Referring to for example Helv.Chim.Act.1998,81(7) volume, the 1207th page.
Those skilled in the art recognize, various functional groups can be transformed into other, so that the compound of different formula 1 to be provided.For example, the intermediate of the compound of preparation formula 1 can comprise aromatic nitro, and it can be reduced into amino, then via reaction well known in the art, as Sandmeyer, reacts, and is converted into various halide, so that the compound of formula 1 to be provided.By similar known reaction, aromatic amine (aniline) can be transformed into phenol via diazol, and then it can be had by alkylation the compound of the formula 1 of alkoxy substituent with preparation.Similarly, react the aromatic halide of preparation by Sandmeyer, as bromide or iodide can be under the copper catalytic conditions and alcohol, as Ullmann reaction or its known modification react to provide the compound of the formula 1 that comprises alkoxy substituent.In addition, some halogen group as fluorine or chlorine, can be replaced so that the compound of the formula 1 that comprises corresponding alkoxy substituent to be provided by alcohol under alkali condition.
Above-mentioned reaction also can be in many cases sequentially to carry out in turn, as the preparation of 1H pyrazoles can be by the reaction that is used for scheme 2 about the common preparation feedback of pyrazoles replaced exemplified below.
It should be understood that some reagent of the above-mentioned compound for the preparation of formula 1 and reaction condition may be not with intermediate in some functional group of existing compatible.In these cases, by protecting/going, protect sequence or functional group's tautomeride to add in synthetic will to contribute to obtain desired product.Blocking group use and select to the technical staff of the field of chemical synthesis will be apparent (referring to for example Greene, T.W.Wuts, P.G.M.Protective Groups in Organic Synthesis, second edition; Wiley:New York, 1991).Person of skill in the art will appreciate that, in some cases, after appointment reagent is introduced in the description according in any independent scheme, may need to implement additional conventional synthesis step the synthesizing with perfect 1 compound of not describing in detail.Those skilled in the art also will recognize, the different order of concrete order shown in the time of may be with the compound from preparation formula 1 is implemented the above combination of the step shown in scheme.Those skilled in the art also will recognize, the compound of formula 1 as herein described and intermediate can experience various electrophilic reactions, necleophilic reaction, radical reaction, organometallic reaction, oxidation reaction and reduction reaction, to introduce substituting group or to modify existing substituting group.
Without further elaborating, it is believed that those skilled in the art uses above said content to utilize the present invention to greatest extent.Therefore, below to be interpreted as be only illustrative to synthetic example, and the disclosure do not limited the present invention in any way.Below the step in synthetic example shows the process of each step in whole synthetic conversion, and needn't the concrete preparation process in other example or step be made by process prescription for the raw material of each step.Percentage all by weight, chromatographic solvent mixture or except as otherwise noted only.Except as otherwise noted, the umber of chromatographic solvent mixture and percentage are all by volume.Except as otherwise noted, 1h NMR composes by tetramethylsilane at CDCl 3in with low the report of ppm; " s " means that unimodal, " m " means that multimodal, " br s " mean wide unimodal.Mass spectrum (MS) is as passing through to described molecule addition H +the molecular weight report of (molecular weight is 1) the highest formed isotope abundance parent ion (M+1), adopt APCI (AP +) by mass spectrograph, observe, wherein " amu " represents the mass unit of atom.Reported comprise one or more low abundance (as 37c1, 81br) than the existence of the isotopic molecular ion of high atomic weight." LC/MS " relates to by the combination of liquid chromatography physical separation chemical compound and the compound that separates by the mass spectrograph quality analysis.
synthetic example 1
the chloro-4-fluorophenyl of preparation 4-(2-)-N-(2, the fluoro-4-anisyl of 6-bis-)-1,3-dimethyl-1H- pyrazoles-5-amine (compound 3)
steps A: the chloro-4-fluorophenyl of preparation 4-[2-]-1,3-dimethyl-1H-pyrazoles-5-amine
Dry solid sodium ethanol (Aldrich, 10.2g, 150mmol) suspension in the mixture of dimethylbenzene (60mL) and absolute ethyl alcohol (25mL) stirs under 70 ℃, and through 20 minutes, during the chloro-4-fluorophenyl acetonitrile of 2-(16.96g, 100mmol) is dropped to hot reactant mixture in the mixture of ethyl acetate (30mL) and ethanol (5mL).Described reactant mixture is heated to 3h under 75-78 ℃, then make it cooling.Add water (50mL) with dissolved solid.Be extracted with ethyl acetate mixture once and abandon extract.Aqueous hydrochloric acid by adding 1N to pH2, is then used ethyl acetate (50mL) extraction by aqueous phase as acidified.Dry (MgSO 4) ethyl acetate also evaporation mutually, so that the solid of the chloro-4-fluorophenyl acetonitrile of midbody product α-acetyl group-2-(14.8g) to be provided.
The part (4.61g, 21.8mmol) of the product above obtained stirs in ethanol (15mL), and adds glacial acetic acid (3mL) and methyl hydrazine (1.17mL, 21.8mol).Stir this reactant mixture and heated overnight under refluxing.Then concentrated reaction mixture under reduced pressure, and the residue of gained is pulverized with ethyl acetate.The solid of gained is collected on frit and at air drying, so that the white solid of title compound (2.42g) to be provided.
1H?NMRδ7.2-7.3（m,2H），7.0（m,1H），3.7（s,3H），3.4（br?s,2H），2.1（s,3H）。MS:240amu（AP +）。
step B: the chloro-4-fluorophenyl of the preparation bromo-4-(2-of 5-)-1,3-dimethyl-1H-pyrazoles
Copper bromide (II) (3.94g, 17.7mmol) be added to the chloro-4-fluorophenyl of 4-[2-]-1, the 3-dimethyl-the 1H-pyrazoles-5-amine (, the product of steps A) in (2.4g, 10mmol) solution in acetonitrile (50mL), and described mixture is stirred, and in cooling in ice-water bath, drip t butyl nitrite (90% technical grade, 2.33mL, 17.7mmol) through 5min.Make described reactant mixture slowly be warmed to environmental temperature.Add the HCl aqueous solution (20mL), then add ethyl acetate (20mL).This mixture is by 2-cm's
Figure BDA00002868169000521
diatomaceous filter aid cushion block filters.Described ethyl acetate (20mL) washing for filtering pading block, and separate described phase.Aqueous hydrochloric acid solution and the salt water washing of 1.0N for described organic facies, through MgSO 4dry and concentrated, to stay the terra-cotta semisolid of title compound (2.8g).
1H?NMRδ7.18-7.25（m,2H），7.04（m,1H），3.89（s,3H），2.14（s,3H）。
step C: the chloro-4-fluorophenyl of preparation 4-(2-)-N-(2, the fluoro-4-anisyl of 6-bis-)-1,3-bis- methyl isophthalic acid H-pyrazoles-5-amine
The chloro-4-fluorophenyl of the bromo-4-(2-of 5-)-1,3-dimethyl-1H-pyrazoles, (that is, the product of step B) (0.20g, 0.66mmol), acid chloride (II) (15mg, 0.066mmol), 4, two (diphenylphosphino)-9 of 5-, 9-dimethyl oxa-anthracene (76mg, 0.13mmol) and pulverous potash (1.8g, 13mmol) be blended in anhydrous Isosorbide-5-Nitrae-dioxane (3mL), and described mixture N 2air-flow is aeration 10min under liquid level.The disposable fluoro-4-aminoanisole of 2,6-bis-(0.22g, 1.3mmol) that adds, and add thermal reaction mixture 22h under refluxing.Reactant mixture is passed through
Figure BDA00002868169000531
super-cell filters, and described ethyl acetate (20mL) washing for filtering pading block.Described filtrate water (10mL) and salt solution (10mL) washing, through MgSO 4dry and concentrated, to stay semi-solid residue.This residue, by column chromatography, by the silica gel of 5g, is purified with gradient hexane/ethyl acetate (20:1 to 1:3) wash-out, so that the light brown solid of title compound (48mg) to be provided.
1H?NMRδ7.0-7.1（m,2H），6.85（m,1H），6.26（m,2H），4.84（br?s,1H），3.78（s,3H），3.66（s,3H），2.08（s,3H）。MS:382amu（AP +）。
synthetic example 2
preparation 4-(2, the fluoro-4-anisyl of 6-bis-)-1,3-dimethyl-N-(2,4,6-trifluorophenyl)-1H- pyrazoles-5-amine (compound 7)
steps A: prepare the fluoro-4-p-methoxybenzeneacetonitrile of 2,6-bis-
By KCN(0.88g, 13mmol) solution that is dissolved in water (2mL) drop to water-bath cooling 2,6-bis-fluoro-4-methoxyl group cylite (2.50g, 10.5mmol) is in the solution of DMF (10mL).Described reactant mixture is stirred 20 minutes.Add water (20mL), then reactant mixture is poured over to saturated NaHCO 3in the aqueous solution (20mL) and with ether (50mL), extract.Described organic facies water (5 * 25mL) washing, through MgSO 4dry and concentrated, the oil of crystallization while placing to be provided at, thus the solid of title compound (1.9g) is provided.
1H?NMRδ6.50（m,2H），3.80（s,3H），3.65（s,2H）。
step B: preparation α-acetyl group-2, the fluoro-4-p-methoxybenzeneacetonitrile of 6-bis-
Solid sodium ethanol (4.7g, 66mmol) is stirred in the mixture of dimethylbenzene (20mL) and ethanol (10mL), and be heated to 50 ℃.Drip the solution of the fluoro-4-p-methoxybenzeneacetonitrile of 2,6-bis-(that is, the product of steps A) (8.0g, 44mmol) in ethyl acetate (10.4mL).At 50 ℃ of heating 4h, then make it be cooled to room temperature described reactant mixture.By (100mL) in described reactant mixture impouring water and extract with ethyl acetate (25mL).Described water is acidified to pH4 with the moisture HCl of 3N, and extracts with ethyl acetate (100mL).This organic facies water (50mL), salt solution (50mL) washing, then pass through MgSO 4dry and concentrated, to stay the sepia semisolid of title compound (8.0g).
1H?NMRδ6.56（m,2H），4.86（s,1H），3.83（s,3H），2.40（s,3H）。
step C: preparation 4-(2, the fluoro-4-anisyl of 6-bis-)-1,3-dimethyl-1H-pyrazoles-5-amine
α-acetyl group-2, the fluoro-4-p-methoxybenzeneacetonitrile of 6-bis-(that is, the product of step B) (8.03g, 35.7mmol) and acetic acid (5mL) stir in ethanol (35mL), and add methyl hydrazine (1.91mL, 35.7mmol).By described reactant mixture heating 16h, cooling under refluxing, then in impouring water (100mL).With ethyl acetate (100mL) extraction gained mixture.Then the aqueous NaOH (50mL) of 1N for described organic facies is salt solution (50mL) washing, through MgSO 4dry and concentrated, to stay solid.By dissolution of solid, in methyl alcohol, and the solution of gained is heated to 45 ℃.Drip water (25mL) and make mixture cooling.Collect described precipitation on frit, so that the white solid of title compound (3.88g) to be provided.
1H?NMRδ6.55（m,2H），3.81（s,3H），3.67（s,3H），3.43（br?s,2H），2.09（s,3H）。
step D: the bromo-4-(2 of preparation 5-, the fluoro-4-anisyl of 6-bis-)-1,3-dimethyl-1H-pyrazoles
Copper bromide (II) (3.81g, 16.9mmol) be added into 4-(2, the fluoro-4-anisyl of 6-bis-)-1,3-dimethyl-1H-pyrazoles-5-amine (that is, the product of step C) (3.88g, 15.4mmol) in the solution of acetonitrile (50mL), and stir described mixture, and, in cooling in ice-water bath, through 5min, drip tert-butyl nitrite (90% technical grade, 3.54mL, 26.9mmol).Make described reactant mixture slowly be warmed to environmental temperature.Add the aqueous solution (25mL) of hydrochloric acid, then add ethyl acetate (25mL).And the gained mixture is by 2-cm's
Figure BDA00002868169000551
diatomaceous filter aid cushion block filters.Described ethyl acetate (50mL) washing for filtering pading block, and separate described phase.The HCl aqueous solution (25mL) and salt solution (25mL) washing of 1N for described organic facies, through MgSO 4dry and concentrated.Described residue column chromatography, by the silica gel of 24g, by the hexane/ethyl acetate (9:1 to 1:1) of gradient) wash-out purifies, so that the white solid of title compound (3.25g) to be provided.
1H?NMRδ6.54（m,2H），3.88（s,3H），3.83（s,3H），2.16（s,3H）。
step e: preparation 4-(2, the fluoro-4-anisyl of 6-bis-)-1,3-dimethyl-N-(2,4,6-trifluoro-benzene base)-1H-pyrazoles-5-amine
By the bromo-4-(2 of 5-, the fluoro-4-anisyl of 6-bis-)-1,3-dimethyl-1H-pyrazoles (that is, the product of step D) (0.30g, 0.94mmol), acid chloride (II) (20mg, 0.090mmol), 4, two (diphenylphosphino)-9 of 5-, 9-dimethyl oxa-anthracene (0.11g, 0.19mmol) and pulverous potash (2.6g, 19mmol) in anhydrous Isosorbide-5-Nitrae-dioxane (4mL), mix, and the mixture N of gained 2air-flow is aeration 10min under liquid level.Disposable add 2,4,6-trifluoromethyl aniline (0.28g, 1.9mmol) and in nitrogen, reflux under add thermal reaction mixture 22h.Cooling described reactant mixture, then pass through
Figure BDA00002868169000552
diatomaceous filter aid filters.Described ethyl acetate (20mL) washing for filtering pading block, and described filtrate water (10mL) and salt solution (10mL) washing, through MgSO 4dry and concentrated, to stay semi-solid residue.Described residue column chromatography, by the silica gel of 12g, by the hexane/ethyl acetate (20:1 to 1:3) of gradient) wash-out purifies, so that the semisolid of title compound (73mg) to be provided.
1h NMR(acetone-d 6) δ 6.84(br s, 1H), 6.68(m, 2H), 6.43(m, 2H), 3.77(s, 3H) and, 3.75(s, 3H), 1.99(s, 3H).MS:384amu（AP +）。
synthetic example 3
the chloro-4-fluorophenyl of preparation 4-[[4-(2-)-1,3-dimethyl-1H-pyrazoles-5-yl] oxygen]-3, the 5-difluorobenzene formonitrile HCN (compound 13)
steps A: preparation 4-[(1,3-dimethyl-1H-pyrazoles-5-yl) oxygen]-3, the 5-difluorobenzonitrile
Add potash (1.38g, 10mmol) to 2,4-dihydro-2,5-dimethyl-3H-pyrazoles-3-ketone (0.70g, 6.3mmol) is in the solution of DMF (15mL).Add 3,4,5-trifluoro-benzene formonitrile HCN (0.94g, 6.0mmol), and reactant mixture heats 16h in blanket of nitrogen under 75 ℃, then make it cooling.Described reactant mixture is being distributed between water (60mL) and ethyl acetate (30mL).Described organic facies water (2 * 30mL) and salt solution (30mL) washing, through MgSO 4dry and concentrated, so that the yellow oil of title compound (1.38g) to be provided.
1H?NMRδ7.36（m,2H），5.24（s,1H），3.78（s,3H），2.16（s,3H）。
step B: prepare the fluoro-4-[(4-of 3,5-bis-iodo-1,3-dimethyl-1H-pyrazoles-5-yl) oxygen] benzonitrile
4-[(1,3-dimethyl-1H-pyrazoles-5-yl) oxygen]-3, the 5-difluorobenzonitrile is (, the product of steps A) (1.38g, 5.5mmol) solution in acetonitrile (20mL) stirs at ambient temperature, and the disposable N-iodine succinimide (1.35g, 6.0mmol) that adds.By described reactant mixture heating 2h, cooling under refluxing, then in impouring water (40mL).With ethyl acetate (40mL) extraction gained mixture.Described organic facies water (20mL) and saturated NaHCO 3the aqueous solution (20mL) washing, through MgSO 4dry and under reduced pressure concentrated, so that the sepia solid of title compound (2.1g) to be provided.
1h NMR(acetone-d 6) δ 7.80(m, 2H), 3.82(s, 3H), 2.09(s, 3H).MS:376amu（AP +）。
step C: the chloro-4-fluorophenyl of preparation 4-[[4-(2-)-1,3-dimethyl-1H-pyrazoles-5-yl] oxygen]- 3,5-difluorobenzonitrile
To 3, the fluoro-4-[(4-of 5-bis-iodo-1, 3-dimethyl-1H-pyrazoles-5-yl) oxygen] benzonitrile is (, the product of step B) (1.0g, 2.67mmol) in 1, solution in 4-dioxane (6mL) adds the chloro-4-fluorobenzoic boric acid of 2-(alternatively, the chloro-4-fluorophenyl of described B-(2-) boric acid) (0.93g, 5.33mmol), dichloro (two) triphenylphosphine palladium (II) (alternatively, described two (triphenylphosphine) palladium (II) dichloride) (93mg, 0.13mmol), potash (0.74g, 5.33mmol) and water (4mL).The mixture of gained is heated to 5h under refluxing, make it cooling and in distribution between water (20mL) and ethyl acetate (20mL).Described organic facies is through MgSO 4dry and concentrated.Described residue, is purified by the gradient hexane/ethyl acetate by chromatography on silica gel, to obtain the pale solid of title compound (110mg).
1H?NMRδ7.00-7.09（m,3H），6.97（m,1H），6.86（m,1H），3.85（s,3H），2.02（s,3H）。
synthetic example 4
preparation 4-(2, the 4-dichlorophenyl)-N-(2, the 4-difluorophenyl)-1,3-dimethyl-1H-pyrazoles-5- amine (compound 17)
steps A: preparation α-acetyl group-2, the chloro-N-(2 of 4-bis-, 4-difluorophenyl) phenyl-thioacetamide
2,4-difluorophenyl isothiocyanates (0.27mL, 2.0mmol) is added in the suspension of sodium hydride (60% in mineral oil) (112mg, 2.8mmol) in the cooling ice-water bath under blanket of nitrogen of anhydrous tetrahydro furan (4mL) of stirring.1-(2,4-dichlorophenyl)-the solution of 2-acetone (570mg, 2.8mmol) in oxolane (4mL) is dripped through 5min.Stir the yellow solution 1h of gained under 5-10 ℃.Carefully add water (10mL), and described ethyl acetate (10mL) extraction for reactant mixture.Described water is acidified to pH3 with the moisture HCl of 1N, then uses ethyl acetate (20mL) extraction.Described organic extract water (10mL) and salt solution (10mL) washing, through MgSO 4dry and concentrated, to stay solid.Described for solid hexane/ethyl acetate (2:1) grind, be collected on frit and air-dry, so that the white solid of title compound (240mg) to be provided.MS:373amu（AP +）。
step B: preparation 4-(2,4-dichlorophenyl)-N-(2, the 4-difluorophenyl)-1,3-dimethyl-1H- pyrazoles-5-amine
α-the acetyl group-2 that acetic acid (50 μ L) and methyl hydrazine (41 μ L) is added to stirring, the chloro-N-(2 of 4-bis-, 4-difluorophenyl) phenyl-thioacetamide (238mg, 0.64mmol) is in the suspension of ethanol (4mL).Reactant mixture is heated to 2h under refluxing, and make it cooling.Then use ethyl acetate (10mL) to dilute described reactant mixture and wash with aqueous NaOH (10mL), water (10mL) and the salt solution (10mL) of 1N, through MgSO 4dry and concentrated, to stay solid residue.Described residue column chromatography, by the silica gel of 5g, with hexane/ethyl acetate (2:1 to the 1:1) purifying of gradient, so that the solid of title compound (170mg) to be provided.
1H?NMRδ7.43（s,1H），7.19（m,1H），7.07（m,1H），6.78（m,1H），6.62（m,1H），6.37（m,1H），5.22（br?s,1H），3.70（s,3H），2.18（s,3H）。MS:368amu（AP +）。
synthetic example 5
the chloro-4-fluorophenyl of preparation 4-(2-)-α-(2,4-difluorophenyl)-1,3-dimethyl-1H-pyrazoles-5- methyl alcohol (compound 122)
The chloro-4-fluorophenyl of the bromo-4-(2-of 5-)-1,3-dimethyl-1H-pyrazoles (that is, synthetic example 1, the product of step B) (0.25g, 0.82mmol) be dissolved in anhydrous tetrahydro furan (12mL), and described mixture is cooling under dry ice/acetone batch in blanket of nitrogen.Through within 5 minutes, dripping the hexane solution (2.0M, 0.49mL, 0.98mmol) of n-butyl lithium.After 15 minutes, slowly drip 2,4-difluorobenzaldehyde (0.09mL, 0.82mmol) in the solution of anhydrous tetrahydro furan (3mL), cause described dark red solution to shoal as yellow.After 45 minutes, described reactant mixture is by adding saturated NH 4the Cl aqueous solution (～20mL) quencher, and make it be warmed to environmental temperature.This mixture is extracted with ethyl acetate, and with saturated NH 4the Cl aqueous solution (25mL) is also used the described organic facies of salt water washing, through Na 2sO 4dry and concentrated, to stay the residue of thickness.This residue is by column chromatography, and by silica gel, with gradient ethyl acetate, in hexane, (7% to 10%) wash-out is purified, so that the white semisolid of title compound (109mg) to be provided.
1H?NMRδ7.5（m,1H），7.1（m,2H），7.0（m,1H），6.85（m,2H），6.0（br?s,1H），5.9（s,1H），3.8（s,3H），2.1（s,3H）。MS:367amu（AP +）。
synthetic example 6
preparation 4-[[1,3-dimethyl-4-(2,4,6-trifluorophenyl)-1H-pyrazoles-5-yl] oxygen]-3, the 5-difluoro benzonitrile (compound 8)
steps A: prepare 2,4,6-trifluoro benzene acetic acid methyl esters
Stir at ambient temperature the solution of 2,4,6-trifluoro benzene acetic acid (5.00g, 26.3mmol) in methyl alcohol (25mL), and drip thionyl chloride (6mL ,～3 equivalents), cause the temperature of reactant mixture to reach 60 ℃.Make reactant mixture be cooled to environmental temperature and stir 3h.Under ice-cooled, add water (25mL).With ethyl acetate (2 * 100mL) extraction mixture.Then, the organic facies water (2 *) of mixing, saturated sodium bicarbonate aqueous solution and salt water washing, then dry (MgSO 4).It is concentrated so that the clarified oil of title compound (5.38g) to be provided.
1H?NMRδ6.68（m,2H），3.72（s,3H），3.66（s,2H）。
step B: preparation α-acetyl group-2,4,6-trifluoro benzene acetic acid methyl esters
To what stir in blanket of nitrogen, and two (trimethyl silyl) acid amides lithium (1.0M that the business that is cooled to the internal temperature of-65 ℃ obtains, 21.0mL) tetrahydrofuran solution in dripped 2 through 30 minutes, 4,6-trifluoro benzene acetic acid methyl esters (, the product of steps A) (2.04g, 10.0mmol) is dissolved in the solution in dry tetrahydrofuran (10mL).Described reactant mixture is stirred extra 30 minutes, then keep the temperature of-65 ℃ simultaneously, drip the chloroacetic chloride (0.80mL, 11mmol) of fresh distillation in the solution of dry tetrahydrofuran (3mL).Make described reactant mixture slowly be warmed to environmental temperature, then add water (30mL).With ethyl acetate (60mL) extraction gained mixture.Described water 1N hcl acidifying, and extract with ethyl acetate (60mL).Because thin-layer chromatographic analysis shows that extract comprises obvious polar impurity for the second time except additional required product, thus only for the first time ethyl acetate extract be retained.Described the first ethyl acetate extract is also sequentially used hydrochloric acid, water and the salt water washing of 1N, dry (MgSO 4), and concentrated, so that the clarified oil of title compound (1.86g) to be provided.
1h NMR δ 6.69(m, 2H), 3.7(m, 1H and s, 3H), 1.87(s, 3H); There is the enol form dynamic isomer at 13.2ppm and 4.9ppm trace resonance demonstration.
step C: prepare 1,3-dimethyl-4-(2,4,6-trifluorophenyl)-1H-pyrazoles-5-alcohol
α-acetyl group-2,4, the solution of 6-trifluoro benzene acetic acid methyl esters (that is, the product of step B) (2.46g, 10.0mmol) in methyl alcohol (15mL) is added in methyl hydrazine (0.665mL, 12.5mmol), and described the stirring at ambient temperature 3 days.Add moisture citric acid solution (1M, 10mL), then add water (50mL).With ethyl acetate (2 * 50mL) extraction mixture.Sequentially water and the salt water washing of ethyl acetate extract mixed, dry (MgSO 4), and concentrated to stay yellow solid.This solid suspends in the ethyl acetate (～5mL) of small size, progressively adds the hexane of equal volume, and stirs described suspension 30 minutes.Described solid constituent is collected on frit, by the ethyl acetate/hexane (1:1 and 1:2v:v) of fraction, and make its at air drying so that white solid (1.02g) to be provided.Evaporate described mother liquor as has been described, with ethyl acetate and the hexane of a small amount of volume, process the residue of gained, thereby the solid that comprises title compound (total 1.15g) of additional 0.13g is provided.Analyze the solid display quality 242(AP mixed by LC/MS +) key component and microcomponent, subsequently by anti-phase LC wash-out, also there is 242 quality (AP +), be therefore the constitutional isomer of title compound.The apparent ratio of component is 94:6.
1h NMR(acetone-d 6) δ 6.95(m, 2H), 3.52(s, 3H), 1.98(s, 3H); In this solvent, do not observe the resonance of 5-hydroxyl.
step D: preparation 4-[[1,3-dimethyl-4-(2,4,6-trifluorophenyl)-1H-pyrazoles-5-yl] oxygen]- 3,5-difluorobenzonitrile
1,3-dimethyl-4-(2,4,6-trifluorophenyl)-1H-pyrazoles-5-alcohol (that is, the product of step C) (104mg, 0.43mmol) in anhydrous N, the solution of dinethylformamide (2.5mL) is in blanket of nitrogen, cooling in ice-water-bath, and disposable sodium hydride (60% suspension in mineral oil that adds, 20mg, 0.46mmol).After 15 minutes, disposable 3,4, the 5-trifluoro-benzene formonitrile HCN (101mg, 0.64mmol) that adds.Make reactant mixture reach environmental temperature, then it is heated to 2.5h at 40 ℃.Add water (～10mL), and described mixture is extracted with ethyl acetate (2 *～10mL).Sequentially water (3 * 10mL) and the salt water washing of ethyl acetate extract mixed, dry (MgSO 4), and under reduced pressure concentrated.Chromatography on silica gel (5g), with 2:1 hexane-ethyl acetate mixture wash-out, provide the product (51mg) comprised with the title compound of its constitutional isomer 92:8 mixture.
1H?NMRδ7.1（m,2H），6.5-6.6（m,2H），3.85（s,3H），2.05（s,3H）。MS:380amu（AP+）。
synthetic example 7
the bromo-4-fluorophenyl of preparation 4-(2-)-chloro-6-fluorophenyl of N-(2-)-1,3-dimethyl-1H-pyrazoles-5- amine (compound 240)
steps A: the bromo-4-fluorophenyl of preparation 1-(2-)-2-acetone
Sodium methoxide is mixed with toluene (200mL) in the solution (25%, 34mL, 157mmol) of methyl alcohol.Then use water knockout drum to distill out methyl alcohol under 90 ℃.Solution is cooled to after 70 ℃, by dropping funel, through 20min, is accompanied by mechanical agitation, adds and is dissolved in the bromo-4-fluorophenyl acetonitrile of 2-(21.4g, 100mmol) in ethyl acetate (40mL).At this moment, add additional toluene (150mL), to be conducive to stir out a large amount of lightpink precipitations.Be poured in water by reactant mixture and separate organic facies.The acidifying water also is extracted with ethyl acetate.Dry ethyl acetate is mutually and under reduced pressure concentrated with midbody compound α-acetyl group of being provided as raw oil-bromo-4-fluorophenyl acetonitrile of 2-.
Described raw oil be dissolved in sulfuric acid (60%, 170mL) and the 6.5h that refluxes.Then use hexane (2 * 100mL) to extract described reactant mixture, and the hexane extract water and the salt water washing that mix, dry (MgSO 4) and under reduced pressure concentrated, to produce the yellow oil of title compound (14.7g), it just is not further purified and has used in step C.
1H?NMRδ7.33（m,1H），7.18（m,1H），7.01（m,1H），3.85（s,2H），2.23（s,3H）。
step B: the fluoro-2-isocyanide of the preparation chloro-3-of 1-sulfenyl benzene
Solution to the chloro-6-fluoroaniline of 2-(5.0g, 34mmol) in chlorobenzene in (52mL) adds thiophosgene (thiocarburyl chloride) (5.1g, 45mmol) and DMF(0.27mL).Reaction mixture refluxed 2h, then concentrated to stay the brown oil of title compound (6.15g), it is not further purified for step C.
1H?NMRδ7.18（m,2H），7.07（m,1H）。
step C: the bromo-4-fluorophenyl of preparation 4-(2-)-chloro-6-fluorophenyl of N-(2-)-1, the 3-dimethyl- 1H-pyrazoles-5-amine
Under 0 ℃, through 5 minutes, to potassium tert-butoxide (0.41g, 3.3mmol) in THF(20mL) in solution add the bromo-4-fluorophenyl of 1-(2-)-2-acetone (that is, the product of steps A) (0.70g, 3.0mmol) is in THF(10mL) in solution.Continue to stir 1h, then temperature is dropped to-10 ℃.Through 6 minutes, add the chloro-3-of 1-fluoro-2-isothiocyano benzene (that is, the product of step B) (0.57g, 3.0mmol) in THF(10mL) in solution and stir and continue 15 minutes.Add iodomethane (0.54g, 3.8mmol), and remove cooling bath and comprise the chloro-6-fluorophenyl of the bromo-N-(2-of midbody compound α-acetyl group-2-to provide)-reactant mixture of 4-fluorobenzene thioacetamide.After 5min, add water (0.2mL, 11mmol), glacial acetic acid (0.53mL, 9.1mmol) and methyl hydrazine (0.81mL, 15mmol), and reactant mixture is heated to the 6h that refluxes a succession ofly.Then under reduced pressure concentrated crude reaction mixture and by MPLC(0 to 100% ethyl acetate in hexane as eluent) purifying to be to be provided as the title product of pale solid, compound of the present invention (0.55g).
1H?NMRδ7.24（m,1H），7.04（m,1H），6.95（m,1H），6.87（m,1H），6.78（m,1H），6.68（m,1H），5.45（d,1H），3.80（s,3H），2.10（s,3H）。
By method as herein described and methods known in the art, can prepare disclosed compound in following table.Use following abbreviation in following table: Me means methyl, and MeO means methoxyl group, and EtO means ethyoxyl, and CN means cyano group.Due to symmetry, R 1can with R 3exchange, and R mutually 4can with R 6exchange mutually, if R 1, R 3, R 4and R 6the words that allow of definition.
table 1
Figure BDA00002868169000621
R 4for F, R 5for H, R 6for H, and X is NH.
Figure BDA00002868169000622
Figure BDA00002868169000631
The disclosure also comprises that table 2 is to table 180, and the structure of each table is identical with upper table 1, the row headers that different is in table 1 (i.e. " R 4for F, R 5for H, R 6for H, and X is NH.") by the corresponding row headers hereinafter, replaced.For example, in table 2, rower is entitled as " R 4for F, R 5for H, R 6for F, and X is NH.", and R 4, R 5and R 6defined at table 1 above.Therefore, the article one in table 2 specifically discloses 4-(2, the 6-difluorophenyl)-the N-(2-fluorophenyl)-1,3-dimethyl-1H-pyrazoles-5-amine).
Figure BDA00002868169000632
Figure BDA00002868169000641
Figure BDA00002868169000651
Figure BDA00002868169000661
Figure BDA00002868169000671
preparation/effectiveness
Be selected from the compound of compound, its N-oxide and the salt thereof of formula 1, or comprise and there is at least one mixture as the additional Fungicidal compounds described in summary of the invention (, composition), generally at further composition,, to be used to provide Fungicidal active ingredient in preparation, described composition has at least one annexing ingredient as carrier, and described annexing ingredient is selected from surfactant, solid diluent and liquid diluent.Select preparation or composition components, it is consistent as soil types, humidity and temperature with physical property, method of application and the environmental factor of active component.
The mixture of formulation components (a) (being compound, its N oxide or salt of at least one formula 1) and component (b) (for example being selected from (b1) as above to (b46) and their salt) and/or one or more other biologically active cpds or reagent (being insecticide, other fungicide, nematocide, miticide, weed killer herbicide and other biological reagent) in many ways comprising:
(i) formulation components (a), component (b) and/or one or more other biologically active cpds or reagent separately, and use separately or use with suitable weight ratio simultaneously, be for example in-tank mixing thing form; Perhaps
(ii) with suitable weight ratio, that component (a), component (b) and/or one or more other biologically active cpds or reagent is formulated together.
Useful preparation comprises fluid composition and solid composite.Fluid composition comprises solution (comprising emulsible concentrate), suspension, emulsion (comprising microemulsion and/or suspended emulsion) etc., and they can optionally be crowded into gel.The general type of aqueous liquid composition is the concentrated thing of solubility, suspension-concentrates, capsule suspension liquid, concentrated emulsion, microemulsion and suspended emulsion.The general type of non-aqueous liquid composition is emulsible concentrate, microemulsifiable concentrate, can disperses concentrate and oil dispersion.
The general type of solid composite is dirt powder, powder, particle, piller, pellet, lozenge, tablet, filled with film (comprising seed pelleting) etc., and they can be (" wettable ") of water dispersible or water miscible.The film and the dressing that by film forming solution or flowable suspension, are formed especially can be used for seed treatment.Active component can be sealed by (micro-), and further forms suspension or solid pharmaceutical preparation; Alternatively, the whole preparation that contains active component can be sealed to (or " coating ").Seal and can control or postpone the release of active component.Emulsible particle combines the advantage of emulsible concentrate formulation and dry granular preparation.The high-strength combination owner will be as the intermediate of other preparation.
It should be noted that composition embodiment, wherein make to comprise formula 1(or its N-oxide or its salt) the solid composite particle of compound with the solid composite particle that comprises component (b), mix.These mixtures can further mix with the particle that comprises additional agricultural protection agent.Alternatively; two or more agricultural protection agent (for example the compound of component (a) (formula 1), component (b) compound, be not component (a) or agricultural protection agent (b)) can be mixed in one group of granulated solid composition, the solid composite particle that then with one or more groups, comprises one or more additional agricultural protection agent mixes.The general granulate mixture that the mixing of these particles can be announced in WO94/24861 according to the PCT patent is open, or more preferably according to United States Patent (USP), disclose 6,022, and the single-size in 552 mixes guidance.
During sprayable preparation was dispersed in suitable medium usually before spraying.This type of liquid preparation and solid pharmaceutical preparation are mixed with to the preparation that is easy to dilution in spraying medium (normally water).Sprayed volume can approximately one rise in the scope of several kilolitres in per hectare, but more typically at the about decaliter of per hectare in the scope of several hectolitres.Sprayable preparation can mix with water or another kind of suitable medium in tank, for by air or ground, being applied to the processing leaf, or is administered in the somatomedin of plant.Liquid and dry preparation can direct quantitative add in drip irrigation system, or quantitatively add in furrow between planting season.Liquid and solid pharmaceutical preparation can be before plantation seed treatment the time be applied on the seed of plant of crop and other expectation, in order to protect developmental and other underground plant part and/or leaf by systemic Absorption.
Described preparation will comprise active component, thinner and the surfactant of effective dose usually, and it is in following general scope, and summation is by weight 100%.
Figure BDA00002868169000691
Figure BDA00002868169000701
Solid diluent for example comprises clay for example bentonite, montmorillonite, attapulgite and kaolin, gypsum, cellulose, titanium dioxide, zinc oxide, starch, dextrin, sugar (for example lactose, sucrose), silica, talcum, mica, diatomite, urea, calcium carbonate, sodium carbonate and sodium bicarbonate and sodium sulphate.Typical solid diluent is described in the people's such as Watkins Handbook of Insecticide Dust Diluents and Carriers the 2nd edition (Dorland Books, Caldwell, New Jersey).
Liquid diluent comprises, for example, and water, N, N-dimethyl alkane acid amides (for example DMF), citrene, dimethyl sulfoxide (DMSO), N-alkyl pyrrolidone (for example 1-METHYLPYRROLIDONE), ethylene glycol, triethylene glycol, propane diols, dipropylene glycol, polypropylene glycol, propylene carbonate, butylene carbonate, paraffin (white mineral oil for example, normal paraffin hydrocarbons, isoparaffin), alkylbenzene, Fluhyzon, glycerine, glyceryl triacetate, sorbierite, glycerol triacetate, aromatic hydrocarbons, the dearomatization aliphatic compounds, alkylbenzene, Fluhyzon, ketone is (as cyclohexanone, 2-HEPTANONE, isophorone and 4-hydroxy-4-methyl-2-pentanone), acetic acid esters is (as isoamyl acetate, hexyl acetate, heptyl acetate, octyl acetate, nonyl acetate, acetic acid tridecyl ester and isobornyl acetate), other ester is (as the alkylation lactate, dibasic ester and gamma-butyrolacton), and can be straight chain, side chain, saturated or undersaturated alcohol is (as methyl alcohol, ethanol, normal propyl alcohol, isopropyl alcohol, n-butanol, isobutanol, n-hexyl alcohol, 2-Ethylhexyl Alcohol, n-octyl alcohol, decyl alcohol, isodecanol, i-octadecanol, cetanol, laruyl alcohol, tridecanol, oleyl alcohol, cyclohexanol, tetrahydrofurfuryl alcohol, diacetone alcohol and benzylalcohol).Liquid diluent also comprises and saturated with undersaturated fatty acid, (is generally C 6-C 22) glyceride, for example, as the oil of plant seed and fruit (olive oil, castor oil, linseed oil, sesame oil, corn oil, peanut oil, sunflower oil, raisin seed oil, safflower oil, cottonseed oil, soya-bean oil, rapeseed oil, cocoa butter and palm-kernel oil), animal sources fat (tallow for example, lard, lard, cod-liver oil, fish oil), and their mixture.Liquid diluent also comprises the fatty acid of alkylation (for example methylate, ethylization, butylation), and the hydrolysis of the glyceride that wherein fatty acid can be by plant-derived and animal obtains, and can carry out purifying by distillation.Typical liquid diluent is described in the Solvents Guide the 2nd edition (Interscience, New York, 1950) of Marsden.
Solid composite of the present invention and fluid composition comprise one or more surfactants usually.In the time of in adding to liquid, the surface tension of liquid is modified, the most usually reduced to surfactant (also being called as " surface-active agents ") usually.According to the character of the hydrophilic radical in surfactant molecule and lipophilic group, surfactant can be used as wetting agent, dispersant, emulsifier or defoamer.
Surfactant can be divided into non-ionic surface active agent, anion surfactant or cationic surfactant.The ionic surfactant pack that can be used for composition of the present invention is drawn together but is not limited to: alcohol alkoxylates is such as based on natural alcohol and synthol (it can be side chain or straight chain) and the alcohol alkoxylates that made by alcohol and oxirane, expoxy propane, epoxy butane or their mixtures; Amine ethoxylate, alkanolamide and ethoxylation alkanolamide; Alkoxylated triglyceride, such as soybean oil, castor oil and the rapeseed oil of ethoxylation; The alkylphenol alcoxylates, such as octyl phenol ethoxylate, nonyl phenol ethoxylate, dinonyl phenol ethoxylate and dodecyl phenol ethoxylate (being made by phenol and oxirane, expoxy propane, epoxy butane or their mixtures); The block polymer that oxirane or expoxy propane make and the trans block polymer that wherein end-blocks is made by expoxy propane; Ethoxylated fatty acid; Ethoxylated fat ester and oil; The ethoxylation methyl esters; Ethoxylation triphenyl vinyl phenol (comprising those that are made by oxirane, expoxy propane, epoxy butane or their mixtures); Fatty acid ester, glyceride, the derivative based on lanolin, many ethoxylations ester (such as many ethoxylation dehydrated sorbitols fatty acid ester, many ethoxylated sorbitols fatty acid ester and many ethoxylated glycerols fatty acid ester); Other dehydrated sorbitol derivative, such as sorbitan ester; Polymeric surfactant, such as random copolymer, block copolymer, alkyd peg(polyethylene glycol) resin, grafting or comb-shaped polymer and star-type polymer; Polyethylene glycol (peg); Cithrol; Surfactant based on siloxanes; And sugar derivatives, such as sucrose ester, alkyl polyglycoside and alkyl polysaccharide.
Useful anion surfactant includes but not limited to: alkyl aryl sulphonic acid and salt thereof; Carboxylation alcohol or alkyl phenol ethoxylate; The diphenyl sulfonate derivatives; Lignin and lignin derivative, such as lignosulfonates; Maleic acid or succinic acid or their acid anhydrides; The alkene sulfonic acid ester; Phosphate, such as the phosphate of alcohol alkoxylates, the phosphate of alkylphenol alcoxylates and the phosphate of styryl phenol ethoxylate; Surfactant based on protein; Sarcosine derivative; Styryl phenol ether sulphate; The sulphate of oil & fat acid and sulfonate; The sulphate of ethoxylated alkyl phenols and sulfonate; The sulphate of alcohol; The sulphate of ethoxylated alcohol; The sulfonate of amine and acid amides, such as N, the N-alkyltaurate; The sulfonate of benzene, isopropyl benzene,toluene,xylene and detergent alkylate and tridane; The polycondensation naphthalene sulfonate; The sulfonate of naphthalene and Fluhyzon; The sulfonate of petroleum distillate; Sulphosuccinamate; And sulfosuccinate and their derivative, such as dialkyl sulfosuccinates.
Useful cationic surfactant includes but not limited to: acid amides and ethoxylation acid amides; Amine is such as N-alkyl propane diamine, three propylidene triamines and dipropylene tetramine, and ethoxylated amine, ethoxylation diamines and propoxylation amine (by amine and oxirane, expoxy propane, epoxy butane or their mixture, being made); Amine salt is such as amine acetate and diamine salts; Quaternary ammonium salt, such as quaternary salt, ethoxylation quaternary salt and two quaternary salts; And amine oxide, such as alkyl dimethyl amine oxide and two-(2-hydroxyethyl)-alkyl amine oxide.
What also can be used for the present composition is the mixture of non-ionic surface active agent and anion surfactant, or the mixture of non-ionic surface active agent and cationic surfactant.Nonionic, anion and cationic surfactant and their recommended purposes are disclosed in a plurality of lists of references of having announced, comprise the Division by McCutcheon ' s, The Manufacturing Confectioner Publishing Co. publication " McCutcheon ' s Emulsifiers and Detergents " (North America and international yearbook version); Sisely and Wood, Encyclopedia of Surface Active Agents, Chemical Publ.Co., Inc., New York, those that describe in 1964.And A.S.Davidson and B.Milwidsky " Synthetic Detergents " the 7th edition (John Wiley and Sons, New York, 1987).
Composition of the present invention also can comprise those skilled in the art and be known as the formulation auxiliary agents of auxiliary agent and additive (some of them also can be considered to play solid diluent, liquid diluent or Action of Surfactant).The pH(buffer), growth of microorganism (antimicrobial), product freezing (antifreezing agent), color (dyes/pigments dispersion), wash-out (film forming agent or adhesive), evaporation (anti-evaporant) and other preparation characteristic in the sedimentation (suspending agent) of the formation of foam (defoamer is such as polysiloxane) in process, active component, viscosity (thixotropic thickening agent), container this type of formulation auxiliary agents and additive can references:.Film forming agent comprises for example polyvinyl acetate, VA, PVP-VA copolymer, polyvinyl alcohol, polyvinyl alcohol copolymer and wax.The example of formulation auxiliary agents and additive comprises the Division by McCutcheon ' s, McCutcheon ' the s Volume2:Functional Materials that The Manufacturing Confectioner Publishing Co. publishes, North America and international yearbook version; And PCT discloses those that list in WO03/024222.
Usually by active component being dissolved in solvent or by grinding in liquid or dry thinner during active component mixes composition of the present invention by the compound of formula 1 and any other active component.Can assign to prepare solution by mixing simply described one-tenth, comprise emulsible concentrate.If it is immiscible with water being used as the solvent of the fluid composition of emulsible concentrate, usually add emulsifier to make the solvent that contains active component that emulsification occur when dilute with water.But working medium grinds the wet-milling particle diameter for the active component slurries of 2,000 μ m at the most, to obtain the particle of average diameter lower than 3 μ m.The water-soluble serous particle that can be prepared as finished product suspension-concentrates (referring to for example U.S.3,060,084) or further be processed to form water dispersible by atomized drying.Dry preparation needs the dry grinding step usually, and it produces the average grain diameter in 2 to 10 μ m scopes.Pulvis and powder can pass through to mix, and usually by grinding (for example, with hammer-mill or fluid energy mill), prepare.Can be by active substance be sprayed on the preform particulate vector or by agglomeration technique and prepares particle and pellet." Agglomeration " (Chemical Engineering, on December 4th, 1967,147-48 page referring to Browning; Chemical Engineer ' the s Handbook of Perry, the 4th edition, McGraw-Hill, New York, 1963, the 8-57 pages reach page and WO91/13546 thereafter.Can, as U.S.4, described in 172,714, prepare by pellet.Water dispersible and water-soluble granular can be as U.S.4, and that instructs in 144,050, U.S.3,920,442 and DE3,246,493 prepares.Tablet can be as U.S.5, and what propose in 180,587, U.S.5,232,701 and U.S.5,208,030 prepares.Film can be according to GB2, the instruction preparation in 095,558 and U.S.3,299,566.
About the further information of formulation art, Pesticide Chemistry and Bioscience referring to T.S.Woods, " The Formulator ' sToolbox-Product Forms for Modern Agriculture " in The Food-Environment Challenge, T.Brooks and T.R.Roberts edit, Proceedings of the9th International Congress on Pesticide Chemistry, The Royal Society of Chemistry, Cambridge, 1999, the 120-133 pages.Also, referring to U.S.3, the 235,361,6th hurdle the 16th walks to the 7th hurdle the 19th row and example 10-41; U.S.3, the 309,192,5th hurdle the 43rd walks to the 7th hurdle the 62nd row and example 8,12,15,39,41,52,53,58,132,138-140,162-164,166,167 and 169-182; U.S.2, the 891,855,3rd hurdle the 66th walks to the 5th hurdle the 17th row and example 1-4; The Weed Control as a Science of Klingman, John Wiley and Sons, Inc., New York,, 81-96 page in 1961; The people's such as Hance Weed Control Handbook, the 8th edition, BlackwellScientific Publications, Oxford, 1989; And Developments in formulation technology, PJB publishes, Richmond, UK, 2000.
In following instance, all percentages all is by weight, prepared in a conventional manner by all preparations.Compound in compound number cross index Table A.Without further performance, it is believed that and adopt above-described those skilled in the art can maximally utilise the present invention.Therefore following instance is interpreted as only illustrating, and the disclosure do not limited the present invention in any way.Percentage is for by weight, unless otherwise indicated.
example A
the high strength concentrate
Figure BDA00002868169000741
example B
wettable powder
Figure BDA00002868169000742
example C
particle
Figure BDA00002868169000743
example D
extrude pellet
Figure BDA00002868169000751
example E
emulsible concentrate
example F
microemulsion
Figure BDA00002868169000753
example G
seed treatment
Figure BDA00002868169000754
Figure BDA00002868169000761
example H
emulsible concentrate
Compound 239 10.0%
Polyoxyethylene sorbitol six oleates 20.0%
C 6-C 10fatty acid methyl ester 70.0%
Usually dilute with water preparation, as those in the preparation table, to form Aquo-composition before using.The Aquo-composition (for example aerosol can composition) that directly applies to plant or its part usually comprise at least about 1ppm or more (for example 1ppm to 100ppm) according to Fungicidal active compound of the present invention.
The example of component (b) Fungicidal compounds comprises diazosulfide-S-methyl, cartap, hot azoles mepanipyrim (ametoctradin), amisulbrom, anilazine, penta ring azoles, Fluoxastrobin, M 9834, M 9834-M, benodanil, benomyl, the benzene metsulfovax, the cumene metsulfovax, diclomezin, binapacryl, biphenyl, Bitertanol, wide-spectrum bactericide, blasticidin S-S, Boscalid, bromuconazole, bupirimate, the fourth Saite, carboxin, ring propionyl bacterium amine, difoltan, captan, carbendazim, chloroneb, tpn, chlozolinate, clotrimazole, mantoquita, as bordeaux mixture (ternary copper sulphate), Kocide SD and Cupravit, the match seat goes out, cyflufenamid, frost urea cyanogen, Cyproconazole, cyprodinil, Euparen, two chlorine zarilamids, diclomezine, botran, the mould prestige of second, Difenoconazole, the difluoro woods, Milcurb, dimethomorph, dimoxystrobin, alkene azoles alcohol, alkene azoles alcohol-M, karathane, the Delan, dodemorph, dodine, edifenphos, Enestroburin, epoxiconazole, etaconazole, Guardian, the phonetic phenol of second, Grandox fumigant,
Figure BDA00002868169000762
cycloheximide triazole, Fenamidone, Fenarimol, RH-7592, first furan anilide, fenhexamid, zarilamid, fenpiclonil, fenpropidin, butadiene morpholine, amine benzene pyrrole bacterium ketone, fentin acetate, triphenyl tin chloride, triphenyl tin hydroxide, ferbam, ferimzone, fluazinam, fludioxonil, fluorine acyl bacterium amine, flumorph, fluopicolide (also being known as fluopicolide), fluorine pyrrole bacterium acid amides, the fluorine acid imide, fluoxastrobin, Fluquinconazole, Flusilazole, flusulfamide, clean (the fluoro-5-(trifluoromethyl of the 2-[[2-) phenyl of fluorine thiophene bacterium] sulphur]-the 2-[3-(2-anisyl)-the inferior thiazolidinyl of 2-] acetonitrile), flutolanil, Flutriafol, fluorobenzene pyrrole bacterium amine (fluxapyroxad), folpet, phosethyl-Al, furidazol, furalaxyl, good fortune Lapie, own azoles alcohol, dislike mould spirit, gram heat is clean, imazalil, the acid amides azoles, iminoctadine, iodo propinyl butyl carbamate, plant the bacterium azoles, iprobenfos, iprodione, Propineb, Isoprothiolane, naphthalene pyrrole bacterium amine (isopyrazam), isotianil, kasugarnycin, gram is received glad, mancozeb, mandipropamid, maneb, mebenil, dinocap, metalaxyl, metalaxyl-M, metconazole, methasulfocarb, Carbatene, SSF 126, mepanipyrim, metrafenone, nitrile bacterium azoles, how to replace fragrant, Neo-Asozin (ferric methylarsonate), nuarimol, octhilinone, ofurace, orysastrobin, Wakil,
Figure BDA00002868169000771
quinoline acid,
Figure BDA00002868169000772
imidazoles, oxycarboxin, oxytetracycline, penconazole, Pencycuron, penta benzene pyrrole bacterium amine, the pyrrole metsulfovax, pefurazoate, phosphorous acid and salt thereof, phthalide, ZEN 90160, pipron, polyoxin, allyl isothiazole, prochloraz, procymidone, Propamocarb, propamocarb, propiconazole, Propineb, the third oxygen quinoline, prothioconazoles, pyraclostrobin, azoles amine bacterium ester, azoles bacterium ester, Ppyrazophos, pyrrole bacterium benzene prestige (pyribencarb), pyributicarb, pyrifenox, phonetic mould amine, methoxy benzene pyridine bacterium (pyriofenone), pyroquilon, pyrrolnitrin, the quinoline azoles, chinomethionat, fast promise sweet smell, pcnb, encircle the third pyrrole bacterium amine (sedaxane), Silthiopham, simeconazoles, volution bacterium amine, streptomycin, sulphur, Tebuconazole, isobutyl ethoxyquin (tebufloquin), gram is withered rotten, tecnazene, Terbinafine, fluorine ether azoles, probenazole, the thiophene furan goes out, topsin, thiophanate-methyl, arasan, tiadinil, tolelofos-methyl, tolyfluanid, triazolone, Triadimenol, triarimol, azoles bacterium piperazine, tricyclazole, tridemorph, fluorine bacterium azoles, tricyclazole, oxime bacterium ester, triforine, Trimorfamid Fademorf, triticonazole, uniconazole P, jinggangmeisu, downy mildew go out (downy mildew goes out), vinclozolin, zineb, ziram, oxamides, the chloro-3-(trifluoromethyl of N'-[4-[4-) phenoxy group]-2, the 5-3,5-dimethylphenyl]-N-ethyl-N-methyl azomethine acid amides, the chloro-6-(2 of 5-, 4,6-trifluorophenyl)-7-(4-methyl piperidine-1-yl) [1,2,4] triazols [1,5-a] pyrimidines (BAS600), the N-[2-[4-[[3-(4-chlorphenyl)-2-propine-1-yl] oxygen]-the 3-anisyl] ethyl]-3-methyl-2-[(methylsulfonyl) amino] butyramide, the N-[2-[4-[[3-(4-chlorphenyl)-2-propine-1-yl] oxygen]-the 3-anisyl] ethyl]-3-methyl-2-[(ethylsulfonyl) amino] butyramide, 2-butoxy-6-iodo-3-propyl group-4H-1-benzopyran-4-one, the 3-[5-(4-chlorphenyl)-2,3-dimethyl-3-is different
Figure BDA00002868169000773
azoles quinoline base] pyridine, the N-[1-[[[1-(4-cyano-phenyl) ethyl] sulfonyl] methyl] propyl group] carbamic acid-4-fluorobenzene ester, the N-[[(cyclo propyl methoxy) amino] [the 6-(difluoro-methoxy)-2, the 3-difluorophenyl] methylene] phenyl acetamide, α-(methoxyimino)-N-methyl-2-[[[1-[3-(trifluoromethyl) phenyl] ethyoxyl] imino group] methyl] phenyl acetamide, the chloro-3-(trifluoromethyl of N'-[4-[4-) phenoxy group]-2, the 5-3,5-dimethylphenyl]-N-ethyl-N-methyl azomethine acid amides, the chloro-2-nitrobenzophenone of N-(4-)-N-ethyl-4-methyl benzenesulfonamide, 2-[[[[3-(2, the 6-dichlorophenyl)-1-methyl-2-propylene-1-subunit] amino] oxygen] methyl]-α-(methoxyimino)-N-methylbenzene acetamide, 1-[(2-propylene sulfenyl) carbonyl]-the 2-(1-Methylethyl)-the 4-(2-aminomethyl phenyl)-5-amino-1H-pyrazoles-3-ketone, ethyl-6-octyl group-[1, 2, 4] triazol [1, 5-a] pyrimidin-7-ylamine, N-[4-[[[[(1-methyl isophthalic acid H-tetrazolium-5-yl) phenylmethylene] amino] oxygen] methyl]-the 2-thiazolyl] amyl carbamate, N-[6-[[[[(1-methyl isophthalic acid H-tetrazolium-5-yl) phenylmethylene] amino] oxygen] methyl]-the 2-pyridine radicals] amyl carbamate, the bromo-6-quinolyl of 2-[(3-) oxygen]-N-(1, 1-dimethyl-2-butine-1-yl)-2-(methyl mercapto) acetamide, 2-[(3-acetenyl-6-quinolyl) oxygen]-the N-[1-(methylol)-1-methyl-2-propine-1-yl]-the 2-(methyl mercapto) acetamide, N-(1, 1-dimethyl-2-butine-1-yl)-2-[(3-acetenyl-6-quinolyl) oxygen]-the 2-(methyl mercapto) acetamide and N'-[4-[[3-[(4-chlorphenyl) methyl]-1, 2, 4-thiadiazoles-5-yl] oxygen]-2, the 5-3,5-dimethylphenyl]-N-ethyl-N-methyl azomethine acid amides.It should be noted that aforementioned inventory does not also comprise the N'-[4-[[3-[(4-chlorphenyl) methyl]-1,2,4-thiadiazoles-5-yl] oxygen]-2, the 5-3,5-dimethylphenyl]-N-ethyl-N-methyl azomethine acid amides.Also noteworthy is that, aforementioned inventory does not also comprise fourth Saite, etaconazole, quinoline azoles, triarimol, the bromo-6-quinolyl of 2-[(3-) oxygen]-N-(1,1-dimethyl-2-butine-1-yl)-2-(methyl mercapto) acetamide, 2-[(3-acetenyl-6-quinolyl) oxygen]-the N-[1-(methylol)-1-methyl-2-propine-1-yl]-the 2-(methyl mercapto) acetamide and N-(1,1-dimethyl-2-butine-1-yl)-2-[(3-acetenyl-6-quinolyl) oxygen]-the 2-(methyl mercapto) acetamide.
It should be noted that, as the Fungicidal compounds in composition component of the present invention (b), it is Fluoxastrobin, gram is received glad, oxime bacterium ester, pyraclostrobin, azoles amine bacterium ester, azoles bacterium ester, ZEN 90160, dimoxystrobin, SSF 126/SSF 126, carbendazim, tpn, fast promise sweet smell, metrafenone, methoxy benzene pyridine bacterium (pyriofenone), cyflufenamid, fenpropidin, butadiene morpholine, bromuconazole, Cyproconazole, Difenoconazole, epoxiconazole, etaconazole, RH-7592, Flusilazole, fluorobenzene pyrrole bacterium amine (fluxapyroxad), own azoles alcohol, plant the bacterium azoles, metconazole, nitrile bacterium azoles, penconazole, propiconazole, the third oxygen quinoline, prothioconazoles, Tebuconazole, triticonazole,
Figure BDA00002868169000781
cycloheximide triazole, prochloraz, pyrrole metsulfovax and Boscalid (Boscalid).
General plant disease (as lower utilization rate or wider phytopathogen control range) or the resistance caused by plant pathogenic fungi for better control managed the preferably compound of formula 1, the mixture of its N-oxide or its salt, it has the Fungicidal compounds that is selected from following group: Fluoxastrobin, gram is received glad, oxime bacterium ester, pyraclostrobin, azoles amine bacterium ester, azoles bacterium ester, ZEN 90160, dimoxystrobin, SSF 126/SSF 126, fast promise sweet smell, metrafenone, cyflufenamid, fenpropidin, butadiene morpholine, Cyproconazole, Difenoconazole, epoxiconazole, etaconazole, Flusilazole, metconazole, nitrile bacterium azoles, propiconazole, the third oxygen quinoline, prothioconazoles, methoxy benzene pyridine bacterium (pyriofenone), Tebuconazole, triticonazole,
Figure BDA00002868169000791
cycloheximide triazole and pyrrole metsulfovax.
In Fungicidal composition of the present invention, component (a) (that is, at least one compound is selected from compound, its N-oxide and salt thereof of formula 1) and component (b) exist with the antifungal effective dose.The weight ratio of component (b) (that is, one or more additional Fungicidal compounds) and component (a) generally between about 1:3000 between about 3000:1, and more typical between about 1:500 and about 500:1.Table B1 has listed and has related to typical, the more typical and most typical ratio ranges of the concrete Fungicidal compounds of component (b).Table A 1 to A43 and C1 to C43 for example understand the weight ratio for the concrete combination of Fungicidal compounds.It should be noted that wherein component (a) is the composition of about 125:1 to about 1:125 with the weight ratio of component (b).Fungicidal compounds with many components (b), these compositions especially are effective to control the plant disease caused by fungal plant pathogen.Especially it should be noted that wherein component (a) is extremely about 1:25 of about 25:1 with the weight ratio of component (b), or about 5:1 is to the composition of about 1:5.Those skilled in the art can easily determine by simple experiment the necessary Fungicidal compounds of desired scope of weight ratio and amount of application protect and control to(for) antifungal.It is evident that, in component (b), comprise that additional Fungicidal compounds can enlarge controlled plant disease scope and surmount the scope of being controlled by independent component (a).
Concrete mixture (compound number relates to the compound in concordance list A) is listed in Table A 1 to A43.In Table A 1, the every row below column headings " component (a) " and " component (b) " discloses particularly as compound 3 components (a) mixture, and described composition has the Fungicidal compounds of component (b).Entry under title " illustrative ratio " discloses three concrete weight ratios of component (b) about disclosed mixture and component (a).For example, the first row of Table A 1 discloses the mixture of compound 3 with my acid benzene-S-methyl, and lists my acid benzene-S-methyl and 1:1, the 1:4 of compound 3 or the weight ratio of 1:18.
table A 1
Figure BDA00002868169000792
Figure BDA00002868169000801
Figure BDA00002868169000811
Figure BDA00002868169000831
Figure BDA00002868169000851
(*) component (b) is with respect to the weight ratio of component (a)
Each structure of Table A 2 to A43 is with identical in upper Table A 1, and the entry " component (a) " below different is column headings is alternative by the hurdle entry of the respective components (a) shown in hereinafter.Therefore, for example, the entry in Table A 2 below column headings " component (a) " is enumerated as " compound 7 " entirely, and in Table A 2, the first row below column headings specifically discloses the mixture of compound 7 and my acid benzene-S-methyl.Table A 3 to A43 is constructed similarly.
Table B1 has listed the concrete combination of component (b) compound and component (a), illustration mixture of the present invention, composition and method.Concrete component (b) compound (for example " my the acid benzene-S-methyl " of the first row) has been listed on the first hurdle of table B1.Second, third and the 4th hurdle of table B1 listed component (b) compound and usually has been applied to the amount of crops of farmland growth with respect to the weight ratio scope of component (a) (as my acid benzene-S-methyl is " 2:1 to 1:180 " by weight with respect to component (a)).Therefore, the first row institute that for example shows B1 is concrete open, usually with the weight ratio between between 2:1 to 1:180, uses the combination of my acid benzene-S-methyl and component (a).The remaining row of table B1 can be explained similarly.Especially noticeable any one in the compound listed as component (a) and the composition according to disclosed weight ratio mixture of listed compound in table B1 component (b) hurdle in table B1 of being included in embodiment 45.Therefore, table B1 has supplemented and has been disclosed in the concrete ratio had about the Table A 1 to A43 of the ratio ranges of these combinations.
table B1
Figure BDA00002868169000871
Figure BDA00002868169000881
Figure BDA00002868169000891
Figure BDA00002868169000901
Figure BDA00002868169000911
Figure BDA00002868169000921
Figure BDA00002868169000931
As annotated, the present invention comprises embodiment, and wherein said composition comprises component (a) and (b), component (b) comprise at least one two group each be selected from (b1) Fungicidal compounds to (b46).The table C1 to C43 listed concrete mixture (the compound sequence number refers to the index of compound in Table A) to illustrate embodiment, wherein component (b) comprise at least one two group each be selected from (b1) Fungicidal compounds to (b46).In table C1, the every row below column headings " component (a) " and " component (b) " discloses particularly as compound 3 components (a) mixture, and described composition has the Fungicidal compounds of at least two kinds of components (b).Entry below title " illustrative ratio " is to disclose three kinds of concrete weight ratios of component (a) and each component (b) Fungicidal compounds about disclosed mixture sequence.For example, the first row discloses the mixture of compound 3 with Cyproconazole and Fluoxastrobin, and has listed the 1:1:1 of compound 3 with Cyproconazole and Fluoxastrobin, the weight ratio of 2:1:1 or 3:1:1.
table C1
Figure BDA00002868169000941
Figure BDA00002868169000951
Figure BDA00002868169000961
Figure BDA00002868169000971
Figure BDA00002868169000981
(*) in order component (a) with respect to the weight ratio of component (b)
Each structure of table C2 to C43 is with identical in upper table C1, and the entry " component (a) " below different is column headings is alternative by the hurdle entry of the respective components (a) shown in hereinafter.Therefore, for example, in table C2, entry below column headings " component (a) " is enumerated as " compound 7 " entirely, and the first row below table C2 column headings specifically discloses the mixture of compound 7 and Cyproconazole and Fluoxastrobin, with compound 7: Cyproconazole: the illustrative 1:1:1 of Fluoxastrobin, the weight ratio of 2:1:1 and 3:1:1.Table C3 to C43 constructs similarly.
Figure BDA00002868169000982
Figure BDA00002868169000991
It should be noted that composition of the present invention, described composition comprise there is at least one and there is formula 1(or its N-oxide or its salt from other Fungicidal compounds of the different action sites of formula 1 compound) compound.But in some cases, have the similar control scope from least one other Fungicidal compounds combination of different action sites, for resistance, management will be especially favourable.Therefore, composition of the present invention can advantageously comprise at least one Fungicidal active compound, and described Fungicidal active compound is selected from (b1) as above to (b46), and it has similar control range but different action sites.
Component (a) or component (a) can further mix to form the multicomponent insecticide with one or more other bioactive compounds or reagent with the composition of component (b), give the even more agricultural protection of wide spectrum, described bioactive compound or reagent comprise insecticide, the nematocide bactericide, miticide, weed killer herbicide, herbicide-safener, growth regulator is as insect molting inhibitor and the stimulant of taking root, chemosterilants, semiochemical, repellent, attractant, pheromones, feeding stimulant, nutrient for plants, other biologically active cpds or insect malignant bacteria, virus or fungi.Therefore the invention still further relates to composition, the component that described composition comprises the antifungal effective dose (a), or the mixture of component (a) and component (b), and at least one additional bioactive compound or reagent of biologic effective dose, and can comprise at least one surfactant, solid diluent or liquid diluent.Other bioactive compound or reagent also can be configured to separately in the composition that comprises at least one surfactant, solid or liquid diluent.For composition of the present invention, can be by one or more other biologically active cpds or reagent and component (a) and/or (b) formulated together to form pre-composition, perhaps can prepare respectively one or more other biologically active cpds or reagent and component (a) and (b), and preparation is mixed to (for example, in the spraying tank) before application, or alternatively, carry out sequential application.
Can with component (a), or the composition of component (a) and component (b) this type of biologically active cpds formulated together or the example of reagent are: insecticide, as abamectin, orthen, Acetamiprid, acetyl worm nitrile, acrinathrin, Aldicarb, sulfanilamide (SN) mite ester, Amitraz, Avermectin, azadirachtin, gusathion m, Biphenthrin, Bifenazate, bistrifluron, buprofezin, carbofuran, cartap, chinomethionat, chlorfenapyr, UC 62644, Rynaxypyr, Chlorpyrifos, the methyl Chlorpyrifos, the gram chlorobenzene, can fragrant promise, clothianadin, cyanogen insect amide, cyflumetofen, cyfloxylate, β-cyfloxylate, cyfloxylate, γ-cyfloxylate, λ-cyfloxylate, plictran, cypermethrin, cyromazine, Deltamethrin, diafenthiuron, diazinon, dicofol, dieldrin, Hooker HRS 16, diflubenzuron, dimefluthrin, Rogor, MTI-446, two propyl phenyl ethers, Affirm (Merck Co.), 5a,6,9,9a-hexahydro-6,9-methano-2,4, cis fenvalerate, second worm nitrile, second mite azoles, fenamiphos, fenazaquin, fenbutatin oxide, fenothiocarb, fenoxycarb, fenpropathrin, fenpyroximate, nitrile benzene phenothrin, ethiprole, flonicamid, Flubendiamide, flucythrinate, taufluvalinate, phonetic worm amine, flufenoxuron, large good fortune pine, chlorine worm hydrazides, HEXAFLUMURON, Hexythiazox, Hydramethylnon Bait, imicyafos, Imidacloprid, indoxacarb, isofenphos, lufenuron, malathion, chlorine fluorine ether chrysanthemum ester, metaflumizone, Halizan, acephatemet, methidathion, Methomyl, methoprene, methoxychlor, methoxyfenozide, methoxy Bian Flumethrin, the polynactin oxime, nuvacron, nicotine, Nitenpyram, nithiazide, Rimon, polyfluoro worm uride, oxamoyl, parathion, parathion-methyl, Permethrin, thimet, Phosalone, phosmet, phosphamidon, Aphox, Profenofos, the third Flumethrin, propargite (propargite), prothiocarb, propyl benzene hydrocarbon chrysanthemum ester, pymetrozine, the pyrazine ethiprole, pyrethrins, pyridaben, pyridalyl, new quinazoline ditosylate salt insecticide (pyrifluquinazon), the pyridine ethiprole, pyriproxyfen, rotenone, Ryanodine, many flavensomycin, pleocidin, spiral shell mite ester, Spiromesifen, spiral shell worm ethyl ester, fluorine pyridine worm amine nitrile, sulprofos, the worm hydrazides, tebufenpyrad, diflubenzuron, tefluthrin, terbufos, stirofos, etrafluorine ethofenprox, thiacloprid, Diacloden, UC-51762, dimehypo, Tolfenpyrad, tralomethrin, triaguron, chlorophos, the desinsection urea, nematocide is Aldicarb, imicyafos, oxamoyl and fenamiphos for example, bactericide, such as streptomycin, miticide, as Amitraz, chinomethionat, gram chlorobenzene, miticide (cyenopyrafen), plictran, dicofol, Hooker HRS 16, second mite azoles, fenazaquin, fenbutatin oxide, fenpropathrin, fenpyroximate, Hexythiazox, propargite (propargite), pyridaben and tebufenpyrad, and biological agent, comprise for example Δ-endotoxin of sealing of bacillus thuringiensis, bacillus thuringiensis Ku Er Stark subspecies and bacillus thuringiensis (for example Cellcap, MPV, MPVII) of insect malignant bacteria, insect pathogenic fungus, for example green muscardine fungus, with Insect Pathogenic virus, comprise that baculoviral, nuclear polyhedrosis virus (NPV) are such as HzNPV, AfNPV, and PuGV (GV), such as CpGV.
These agronomy protectants (be insecticide, fungicide, nematocide; miticide, weed killer herbicide and biologic product) general list of references comprise that (C.D.S.Tomlin edits " The Pesticide Manual " the 13rd edition, British Crop Protection Council; Farnham, Surrey, U.K.; 2003 and The BioPesticide Manual second edition, L.G.Copping edits, British Crop Protection Council; Farnham; Surrey, U.K., 2001.
For the embodiment that wherein uses one or more these different blending ingredients, the mixture of these different blending ingredients (total amount) and component (a) or component (a) and component (b)) weight ratio usually between about 1:3000 and about 3000:1.It should be noted that between about 1:100 and about 3000:1, or for example, between the weight ratio between about 1:30 and about 300:1 (ratio between about 1:1 and about 30:1).Obviously, comprising these annexing ingredients can make the disease control range surmount the control range of the mixture of component (a) or component (a) and component (b) to disease.
Can by the combined administration of component (a) compound and/or itself and component (b) compound and/or one or more other bioactive compounds or reagent to by genetic transformation with on the plant to invertebrate pests marking protein toxicity (such as bacillus thuringiensis Δ-endotoxin).Outer seedbed is used separately this component (a) or can be worked in coordination with the toxin protein of expressing with the effect of component (b) combined administration.
It should be noted that as described in summary of the invention, comprised component (a) or component (a) and combination (b) or composition, also comprise at least one invertebrate pests control compound or reagent (as, insecticide, miticide).Especially it should be noted that and comprise component (a) and at least one (, one or more) invertebrate pests controls the composition of compound or reagent, and it then can be subsequently mixes to provide with component (b) and comprises component (a) and (b) and the composition of one or more invertebrate pests control compounds or reagent.Alternatively; not initial the mixing with component (b); comprise component (a) and at least one invertebrate pests and control the composition of the biology effective dose of reagent, can be administered to plant or plant seed (directly or by the environment of plant or plant seed) and not be subject to the disease caused by fungal pathogens and the infringement caused by invertebrate pests to protect described plant or plant seed.
For wherein using one or more invertebrate pests to control the embodiment of compound, the weight ratio of these compounds (total amount) and component (a) compound is usually between about 1:3000 and about 3000:1.For example it should be noted that, between the weight ratio between about 1:300 and about 300:1 (ratio between about 1:30 and about 30:1).Those skilled in the art can be easy to determine by simple experiment the biology effective dose of the active component that the desired biologically active scope of acquisition needs.
It should be noted that composition of the present invention, it is except comprising component (a) compound, separately or with component (b) combination beyond, also comprise at least one and be selected from following invertebrate pests and control compound or reagent: abamectin, orthen, Acetamiprid, acetyl worm nitrile, acrinathrin, Aldicarb, sulfanilamide (SN) mite ester, Amitraz, Avermectin, azadirachtin, gusathion m, Biphenthrin, Bifenazate, bistrifluron, buprofezin, carbofuran, cartap, chinomethionat, chlorfenapyr, UC 62644, Rynaxypyr, Chlorpyrifos, the methyl Chlorpyrifos, the gram chlorobenzene, can fragrant promise, clothianadin, cyanogen insect amide, cyflumetofen, cyfloxylate, β-cyfloxylate, cyfloxylate, γ-cyfloxylate, λ-cyfloxylate, plictran, cypermethrin, cyromazine, Deltamethrin, diafenthiuron, diazinon, dicofol, dieldrin, Hooker HRS 16, diflubenzuron, dimefluthrin, Rogor, MTI-446, two propyl phenyl ethers, Affirm (Merck Co.), 5a,6,9,9a-hexahydro-6,9-methano-2,4, cis fenvalerate, second worm nitrile, second mite azoles, fenamiphos, fenazaquin, fenbutatin oxide, fenothiocarb, fenoxycarb, fenpropathrin, fenpyroximate, nitrile benzene phenothrin, ethiprole, flonicamid, Flubendiamide, flucythrinate, taufluvalinate, phonetic worm amine, flufenoxuron, large good fortune pine, chlorine worm hydrazides, HEXAFLUMURON, Hexythiazox, Hydramethylnon Bait, imicyafos, Imidacloprid, indoxacarb, isofenphos, lufenuron, malathion, chlorine fluorine ether chrysanthemum ester, metaflumizone, Halizan, acephatemet, methidathion, Methomyl, methoprene, methoxychlor, methoxyfenozide, methoxy Bian Flumethrin, the polynactin oxime, nuvacron, nicotine, Nitenpyram, nithiazide, Rimon, polyfluoro worm uride, oxamoyl, parathion, parathion-methyl, Permethrin, thimet, Phosalone, phosmet, phosphamidon, Aphox, Profenofos, the third Flumethrin, propargite (propargite), propyl benzene hydrocarbon chrysanthemum ester, pymetrozine, the pyrazine ethiprole, pyrethrins, pyridaben, pyridalyl, new quinazoline ditosylate salt insecticide (pyrifluquinazon), the pyridine ethiprole, pyriproxyfen, rotenone, Ryanodine, many flavensomycin, pleocidin, spiral shell mite ester, Spiromesifen, spiral shell worm ethyl ester, fluorine pyridine worm amine nitrile, sulprofos, the worm hydrazides, tebufenpyrad, diflubenzuron, tefluthrin, terbufos, stirofos, etrafluorine ethofenprox, thiacloprid, Diacloden, UC-51762, dimehypo, Tolfenpyrad, tralomethrin, triaguron, chlorophos, the desinsection urea, Bacillus thuringiensis subspecies.Encapsulated Δ-endotoxin, baculoviral, insect malignant bacteria, Insect Pathogenic virus and the insect pathogenic fungus of bacillus thuringiensis Ku Er Stark subspecies, nuclear polyhedrosis virus, bacillus thuringiensis.It should be noted that above-mentioned inventory does not comprise chlorine fluorine ether chrysanthemum ester, fluorine pyridine worm amine nitrile and etrafluorine ethofenprox.
In some cases, component (a) compound, can cause being greater than additive (that is, collaborative) effect with other biologically active (especially invertebrate pests control) compound or reagent (that is, active component) separately or with the combination of component (b).Reduce and be discharged into the active principle in environment, guarantee effective control of insect simultaneously, be desired always.When invertebrate pest control active component synergy occurs under amount of application, give satisfactory invertebrate pest control level on agronomy, this type of combination can be advantageously used in and reduce the crop production cost, and reduces environmental load.
Table D1 has listed invertebrate pests and has controlled that reagent and compound 3(as component (a) compound determine in concordance list A) illustrative mixture and the concrete combination of composition, described mixture and composition comprise these active components, and use their method according to the present invention.Concrete invertebrate pests controlling agent (for example " abamectin " in the first hurdle) has been listed on table D1 the second hurdle.Table D1 third column has been listed binding mode (if known) or the chemical classes of invertebrate pests controlling agent.Table D1 the 4th hurdle listed described invertebrate pests control amount that reagent uses usually with respect to compound 3 separately or with the embodiment of the weight ratio scope of component (b) combination (as " 50:1 to 1:50 " abamectin by weight with respect to compound 3).Therefore, for example show the D1 the first row specifically open, usually can the combination with abamectin between the weight ratio administered compound 3 between 50:1 to 1:50.The remaining row of table D1 can similarly make an explanation.
table D1
Figure BDA00002868169001041
Figure BDA00002868169001051
Each structure of table D2 to D43 is with identical in upper table D1, and the entry " component (a) " below different is column headings is alternative by the hurdle entry of the respective components (a) shown in hereinafter.Therefore, for example, the entry " component (a) " in table D2 below column headings is enumerated as " compound 7 " entirely, and in table D2, the first row below column headings specifically discloses the mixture of compound 7 and abamectin.Table D3 to D43 constructs similarly.
Figure BDA00002868169001052
Figure BDA00002868169001061
For and an embodiment of the invertebrate pests controlling agent (for example insecticide and miticide) of component (a) compound comprise sodium channel modulators, such as Biphenthrin, cypermethrin, cyfloxylate, λ-cyfloxylate, cyfloxylate, β-cyfloxylate, Deltamethrin, dimefluthrin, cis fenvalerate, nitrile benzene phenothrin, indoxacarb, chlorine fluorine ether chrysanthemum ester, methoxy Bian Flumethrin, the third Flumethrin, pyrethrins, etrafluorine ethofenprox and tralomethrin; Anticholinesterase is Chlorpyrifos, Methomyl, oxamoyl, UC-51762 and triaguron for example; Anabasine is Acetamiprid, clothianadin, MTI-446, Imidacloprid, Nitenpyram, nithiazide, thiacloprid and Diacloden for example; The macrolide insecticides is many flavensomycin, pleocidin, abamectin, Avermectin and Affirm (Merck Co.) for example; The GABA(γ-aminobutyric acid) the chloride channel blocking agent of regulating is 5a,6,9,9a-hexahydro-6,9-methano-2,4, second worm nitrile and ethiprole for example; The chitin synthetic inhibitor is go out clean, flufenoxuron, HEXAFLUMURON, lufenuron, Rimon, polyfluoro worm uride and desinsection urea of buprofezin, match for example; The juvenile hormone analogies are two propyl phenyl ethers, fenoxycarb, methoprene and pyriproxyfen for example; The octopamine receptor part is Amitraz for example; The ecdysone activator is azadirachtin, methoxyfenozide and worm hydrazides for example; The Ryanodine receptors ligand, as Ryanodine, the anthranilic acid diamides, as Rynaxypyr, cyanogen insect amide and Flubendiamide; The similar thing of nereistoxin is cartap for example; The mitochondria electron transfer inhibitor is chlorfenapyr, Hydramethylnon Bait and pyridaben for example; The lipid biosynthesis inhibitor is spirodiclofen and Spiromesifen for example; The cyclodienes insecticide is dieldrin for example; Cyflumetofen; Fenothiocarb; Flonicamid; Metaflumizone; Pyrafluprole; Pyridalyl; Pyridine ethiprole (pyriprole); Pymetrozine; Spiral shell worm ethyl ester; And dimehypo.Comprise that with an embodiment of the biologic product of component (a) compound nuclear polyhedrosis virus is such as HzNPV and AfNPV; Δ-endotoxin of sealing of bacillus thuringiensis and bacillus thuringiensis is Cellcap, MPV and MPVII for example; And the viral insecticide of natural existence and genetic modification, comprise Rhabdoviridae member and insect pathogenic fungus.It should be noted that the composition that comprises component (a) and at least one additional biologically active cpds or reagent, described biologically active cpds or reagent are selected from listed invertebrate pests controlling agent in table D1.
Composition of the present invention can be used as plant disease-controlling agent.Therefore; the present invention also comprises for controlling the method for the plant disease caused by plant pathogenic fungi, and described method comprises to the plant that will protect or its part or uses the present composition (as comprising component (a) or component (a) and composition (b)) of effective dose to the plant seed that will protect or vegetative propagation unit.This aspect of the present invention also is described to the method for the disease that protective plant or plant seed avoid being caused by fungal pathogens; described method comprises the present composition (be applied directly on plant or plant seed, or for example, use by environment (somatomedin)) of using the antifungal effective dose to plant (or its part) or plant seed.
Plant disease control is usually by the part to the protected plant of wish; as root, bar, leaf, fruit, seed, stem tuber or bulb; or the medium (soil or sandy soil) that the protected plant of wish is growing wherein; before infection or after infecting; use effective dose the present composition (as; comprise component (a) or component (a) and mixture (b)), usually used as the composition of preparation, complete.Component (a) or its mixture also can be applied to the rice shoot of seed to protect described seed and to be grown up by described seed.Also can use described mixture by irrigation water, to process plant.
Component (a) (, at least one compound, described compound is selected from compound, its N-oxide and its salt of formula 1) suitable amount of application (as, the antifungal effective dose), and can be subject to many such environmental effects and should determine according to actual service condition for the mixture that comprises according to the present invention component (a) and the suitable amount of application (as the biology effective dose, the antifungal effective dose or insecticidal effective dose) of composition.When to be less than about 1g/ha to approximately 5, when the amount of application of 000g/ha active component is processed, leaf can be protected usually.When with about 0.1g, to the amount of application of every kilogram of seed of about 10g, processing kind of a period of the day from 11 p.m. to 1 a.m, seed and rice shoot can be protected usually; And, when diaspore is processed with the amount of about 0.1 to about 10g every kilogram of diaspore, the diaspore of plant (as transplanted a cutting and stem tuber) can be usually protected.Those skilled in the art can easily determine and provide plant protection and plant disease and optionally the desired scope of other plant pest control is required by simple experiment, the amount of application that comprises component (a) according to the concrete combination of active component of the present invention and composition thereof and composition.
The compound of formula 1, its N-oxide and salt thereof especially are effective to control by fungal pathogens, the plant disease that especially Basidiomycetes and Ascomycetes cause.Mix the disease that these compounds and other Fungicidal compounds can provide control to be caused by Basidiomycetes, Ascomycetes, Oomycete and deuteromycetes broad spectrum fungus phytopathogen.Therefore, mixture as herein described and composition can be controlled broad-spectrum plant disease, crop leaf disease substance, comprising: cereal, such as wheat, barley, oat, naked barley, triticale, paddy rice, corn, Chinese sorghum and millet, vine crop, such as Table Grape and wine grape, field crop, such as rape (draw Kano), sunflower, sugar beet, sugarcane, soybean, peanut (peanut), Nicotiana plant, Alfalfa, clover, shrub lespedeza, trefoil and vetch, pip fruit, such as apple, pears, crabapple, loquat, hawthorn and Wen Bai, stone fruit, such as peach, cherry, plum, apricot, honey peach and almond, citrus fruit, such as lemon, bitter orange, orange, shaddock, mandarin orange (orange) and kumquat, root and stem tuber vegetables and field crop (and their leaf), such as arithoke, table beet and sugar beet, carrot, cassava, ginger, ginseng, horseradish, parsnip, potato, ternip, winter rape, sweet potato, turnip, radish and Chinese yam, bulbous vegetable, such as garlic, leek, onion and green onion, leaf vegetables, such as the bitter dish (rocket salad) of mustard seed, celery, celery, Chinese celery, witloof (thatch dish), fennel, lettuce heads and leaf lettuce, parsley, red witloof (red witloof), rheum officinale, spinach and Swiss chard, Brassicas (cabbage) leaf vegetables, such as broccoli, cauliflower (broccoli), Brussels sprouts, cabbage, Chinese cabbage, cauliflower, wild cabbage, kale, root-mustard, leaf mustard and green vegetable, leguminous vegetables (succulence or without juice), such as lupine, Kidney bean (Phaseolus) (comprises broad bean, kidney bean, lima bean, Kidney bean, the flower beans, scarlet runner bean, snap beans, wide leaf vegetables beans and wax bean), Kidney bean (Vigna genus) (comprises red bean, asparagus bean, cow gram, the crow cowpea, fresh kidney beans, cowpea, cowpea, the moth beans, mung bean, rice bean, cowpea, urd bean and speciality cowpea), broad bean (broad bean), chickpea (Egyptian beans), the melon ear, sword bean, Dolichos lablab, Lens culinaris and pea (Pisum) (comprise kidney bean, sugar pod garden pea, Britain's beans, field pea, pea, green pea, the snow beans, sweet beans, pigeonpea and soybean), fruit vegetable, (comprise bell pepper, red pepper, culinary art pepper, Gan Jiaoshu, pimento such as eggplant, ground-cheery (Physalis), eggplant melon and pepper, blue or green tomato and tomato), the cucurbit vegetables, such as chocho (fruit), wax gourd (wax gourd), citron watermelon, cucumber, gherkin, edible cucurbit (comprising cucurbit, custard squash, sponge gourd and certain herbaceous plants with big flowers), Momordica (comprising balsam apple, dioecism momordica root, balsam pear and Chinese cucumber), muskmelon (comprising muskmelon and pumpkin), custard squash and winter squash (comprising English walnut pumpkin, pumpkin, winter squash, little blue or green pumpkin, noodles melon) and watermelon, soft fruits, such as blackberry, blueberry (comprise the haw certain kind of berries, the Bo Yisen certain kind of berries, reveal the certain kind of berries, short filling blueberry, the purplish blue certain kind of berries, Asian puccoon plum and youngberry), blueberry, Cranberry, currant, synthetism rasp berry, dayberry, the Ou Yue certain kind of berries, the sweet certain kind of berries of sieve, raspberry and strawberry, the tree nut, such as almond, fagus tree nut, Brazil nut, butternut, cashew nut, Chinese chestnut, the short chincapin in North America, fibert (filbert), hickory nut, Hawaii nut, pecan and walnut, tropical fruit (tree) and other crop, such as banana, plantain, mango, coconut, pawpaw, guava, avocado, lichee, american agave, coffee, cocoa, sugarcane, oil palm, sesame, rubber and spices, fiber crop, such as cotton, flax and hemp, turfgrass (comprising warm season and shitivi type turfgrass), such as this spy grass, Kentucky fragrant thoroughwort, buffalograss, Festuca Arundinacea and Bermuda grass.
These pathogene comprise: Oomycete, comprise the Phytophthora pathogene, such as phytophthora infestans, phytophthora sojae kaufmann&gerdemann, the foot rot of citrus bacterium, camphor tree phytophthora and pumpkin epidemic disease bacterium, the rotten mould withered genus pathogene of grass, such as the melon and fruit pythium spp, and the pathogene of downy mildew family, such as Plasmopara viticola, Peronospora (comprising tobacco downy mildew (Peronospora tabacina) and parasitic downy mildew (Peronospora parasitica)), the disease of Pseudoperonospora (Pseudoperonospora) species disease (comprising bacterium of downy mildew of cucumber (Pseudoperonospora cubensis)) and dish stalk mould germ (Bremia lactucae), Ascomycetes, comprise the Alternaria pathogene, such as tomato early blight bacterium and black spot of cabbage bacterium, ball seat Pseudomonas pathogene, such as the grape Guignardia, the Venturia pathogene, such as apple black star bacteria, the Septoria pathogene, such as glume blight bacterium and leaf spoting bacteria, powdery mildew disease pathogene, belong to (comprising wheat powdery mildew) and Erysiphe (comprising the trailing plants Powdery Mildew) such as the Bu Shi white powder, the grape powdery mildew bacterium, powdery mildew of cucumber bacterium and apple mildew bacterium, wheat-based maize ear rot bacterium, grey mold Pseudomonas pathogene, such as the Botrytis cinerea germ, Monilinia fructicola, sclerotium Pseudomonas pathogene, such as Sclerotinia sclerotiorum, Pyricularia oryzae, grape branch rot bacterium, the shape Pseudomonas pathogene of wriggling, such as Exserohilum turcicum, the reticulate pattern germ, the anthracnose substance of falling ill, such as black fruit bacterium or Colletotrichum (as fine strain of millet anthrax bacteria (Colletotrichum graminicola) and watermelon anthrax bacteria (Colletotrichum orbiculare), and gaeumannomyces graminis (Gaeumannomyces graminis), basidiomycetes, comprise the rest fungus disease (such as Puccinia recondita (Puccinia recondita), strip rust bacteria (Puccinia striiformis), leaf rust (Puccinia hordei), puccinia graminis bacterium (Puccinia graminis) and handle rest fungus (Puccinia arachidis)) caused by Rust (Puccinia) species, coffee rest fungus (Hemileia vastatrix) and soybean rest fungus (Phakopsora pachyrhizi), other pathogene comprises Rhizoctonia (Rhizoctonia spp.) species (such as Rhizoctonia solani Kuhn and redness of the skin or complexion sclerotium germ), the Fusarium pathogene, such as pink Fusariumsp, Fusarium graminearum and Fusarium oxysporum, verticillium dahliae (Verticillium dahliae), white thin,tough silk bacterium (Sclerotium rolfsii), moire bacterium (Rynchosporium secalis), black puckery germ (Cercosporidium personatum), alternaria (Cercospora arachidicola) and brown patch germ (Cercospora beticola), sclerotinite (Rutstroemia floccosum) (also is called as coin spot bacterium (Sclerontina homoeocarpa), and other and these closely-related classification of pathogene and bacterial classification.Therefore usually, pathogene is called as disease, and in aforesaid statement, the plant disease that word " pathogene " also refers to be caused by pathogene.More accurately, plant disease is caused by pathogene.Therefore for example, the plant disease of powdery mildew for being caused by the powdery mildew pathogene, the plant disease of Septoria disease for being caused by the Septoria pathogene, and the rust ixodism evil rust ixodism plant disease that substance causes of falling ill of serving as reasons.Some Fungicidal compounds is also for sterilization, and therefore except their Fungicidally active, and described composition or combine also can have antibacterium, such as the activity of erwinia amylovora, xanthomonas campestris, pseudomonas syringae and other relevant bacterial classification.
Significantly, nowadays be found wherein R 2for 2 of the formula 1 of H, (be formula 1, wherein X is NH to aniline-pyrazole compound that 6-replaces, and R 1and R 3h), than R wherein 2it not the pharmacokinetic properties that the compound of the correspondence of H has remarkable improvement.Particularly, in vertebrate, found wherein R 2for H rather than be not that the compound of H has to distribute and enters fat and reduce significantly, thereby reduce the possibility of bioaccumulation.R wherein 2illustrative 2 for the formula 1 of H, the compound 239,240,241,244,245,247,252,253,254,257,258,259,260,261,262,263,264,265,266,267,268,269,270,271,273,275 and 276 of aniline-pyrazole compound that 6-replaces for assert in concordance list A.In addition, except there is more favourable pharmacokinetic properties in vertebrate, found wherein R 1for halogen, or be more specifically Cl or Br, and R 3for F or Cl, or be more specifically F formula 12, phenylamino-pyrazole compound that 6-replaces, work as R 2during for H, to plant fungal disease resistance, such as lipoxygenase, cause, keep significantly high activity.
The pharmacokinetic properties of formula 1 compound can be measured with various Dosimetries known in the pharmacology science.In relating to an illustrative method of single oral dose, three male and three female rats are received and are surveyed the inspection thing via the oral administration gavage.Before being about to administration, then 0.25,0.5,1,2,4,8,12,24h and thereafter every 24h until death, collect the blood of about 0.25mL via the afterbody blood vessel.When death, also collect fat described fat when determining death: the blood plasma ratio.Blood is collected in the pipe that comprises ethylenediamine tetra-acetic acid (EDTA), and with 2500 * g centrifugal in case from blood cell separated plasma.Then for example use acetonitrile and protein precipitation plate (as, Strata Impact protein precipitation plate, Phenomenex, Torrance, CA, the product type CEO-7565 of U.S.A.) follow the instructions that plate provides, extract described blood plasma by protein precipitation.Alternatively, blood plasma is only with acetonitrile extraction, and vortex (that is, using turbine mixer to mix) centrifugal so that protein granulate.After removing protein, by liquid chromatography-mass spectrograph (LC/MS) analysed for plasma about parent compound and/or metabolite.Fat is by organic solvent, such as acetonitrile homogenising extraction.Then analyze extract about parent compound and/or metabolite by LC/MS.Then use non-linear model software as derived from Pharsight, Cary, NC, the WinNonlin of U.S.A. tM) the analysed for plasma pharmacokinetic data is to determine the half life period of the compound of institute's administration in blood plasma, after administration, when reaching maximum plasma concentration (T max) time time, maximum plasma concentration (C max) and plasma concentration area under a curve (AUC).Because the analysis of fat needs rats death, fat number single time point according to this obtains (being the time of rats death).Yet, by using a plurality of rats deaths behind the different interval of medicine feed time, definite this type of parameter for rat is as C max.Use said method, find that the compound 239,240 assert and 241 is than R wherein in concordance list A 2not the compound of the correspondence of H, have to distribute and enter fat and reduce significantly.
In this Fungicidal composition; the compound of formula 1 component (a) can work synergistically with additional component (b) Fungicidal compounds, to provide such as following beneficial effect: the plant disease scope that expansion is controlled, extend preventative and the duration of therapeutic protection and the propagation that suppresses alkaline-resisting fungal pathogens.In a particular embodiment, provide according to composition of the present invention, described composition comprises proportional component (a) and component (b), especially can be used for controlling concrete fungal disease (such as tomato early blight bacterium, wheat powdery mildew, Botrytis cinerea germ, wheat leaf rust germ, Rhizoctonia solani Kuhn, glume blight bacterium, leaf spoting bacteria).
With comparing of expecting based on independent composition activity, Fungicidal mixtures also can provide obviously better disease degree of control.This synergy be described to " in mixture the synergy of two kinds of components can make total effect than two kinds of (or multiple) component effect sums of independent role more greatly or more lasting " (referring to P.M.L.Tames, Neth.J.Plant Pathology1964,70,73-80).Collaboratively therein by the active component that is administered to plant or seed (as, Fungicidal compounds), shown, provide in the method for plant disease control, described active component is to work in coordination with weight ratio and collaborative (effectively collaborative) amount is used.Disease is controlled, is suppressed and not measuring of prevention can surpass 100%.Therefore, basic synergistic expression need to be used the amount of application of active component usually, wherein said active component provides the effect much smaller than 100% individually, so that their additive effect is less than 100% basically so that the possibility increased on effect as synergistic result.On the other hand, the amount of application that active component is too low can not show a lot of activity in mixture, even synergistic beneficial effect is arranged.Those skilled in the art can easily identify and optimize by simple experiment weight ratio and the amount of application (that is, amount) that synergistic Fungicidal compounds is provided.
Below test comprises that test proof the compounds of this invention is for controlling the effect of concrete pathogene; Therefore provide this effect to the Fungicidal mixture that comprises the compounds of this invention.Below test also comprises the control effect of test proof mixture of the present invention on concrete pathogene.Yet disease independent by the compounds of this invention or that provide with mixture is controlled the pathogen bacterial classification that is not restricted to institute's illustration.
The description of compound is referring to concordance list A.Referring to the concordance list B about the fusing point data.Referring to about 1the concordance list C of H NMR data.Abbreviation below using in concordance list subsequently: Me is methyl, and MeO is methoxyl group, and EtO is ethyoxyl, and-CN is cyano group.Due to symmetry, R 1can with R 3exchange, and R mutually 4can with R 6exchange mutually, if R 1, R 3, R 4and R 6the words that allow of definition.Abbreviation " Cmpd. " representative " compound ", and abbreviation " Ex. " representative " example ", and the synthetic example that numeral wherein makes described compound is followed in back.Mass spectrum (M.S.) is as passing through to described molecule addition H +the molecular weight report of (molecular weight is 1) the highest formed isotope abundance parent ion (M+1), used APCI (AP +) by mass spectrograph, observe.The report comprise one or more more low-abundance than the high atomic weight isotope (as 37c1, 81the existence of molecular ion Br).
concordance list A
Figure BDA00002868169001131
Figure BDA00002868169001132
Figure BDA00002868169001141
Figure BDA00002868169001161
Figure BDA00002868169001171
Figure BDA00002868169001181
* fusing point (MP) data are listed in concordance list B.
* AP +data or 1h NMR data are listed in synthetic example.
* * 1h NMR data are listed in concordance list C.
Observation
Figure BDA00002868169001213
parent ion (M), non-M+1 peak value.
Also observation
Figure BDA00002868169001214
402(M+2) peak value.
concordance list B
A fusing point data are ℃.
concordance list C
Figure BDA00002868169001212
Figure BDA00002868169001221
A 1it is unit that H NMR data be take low the ppm number of distance tetramethylsilane.Coupling is called as (s)-unimodal, and (br s's)-wide is unimodal, (ddd)-in pairs doublet, (td)-triple bimodal and (m)-multimodals.
biological example of the present invention
The general approach of test suspension liquid in preparation test A-I: at first the test compounds amount of being dissolved in is equaled in the acetone of final volume 3%, then be suspended in acetone and purified water (by volume 50/50 mixes) surfactant that described purified water comprises with suitable concentration (take ppm as unit)
Figure BDA00002868169001222
the 250014(polyol ester).So the test suspension liquid of gained is used in test A-I.Each test is to carry out in triplicate, and average described result.Spray 200ppm test suspension liquid to running off a little on test plants, be equal to the amount of application of about 800g/ha.Except as otherwise noted, use the evaluation value that means 200ppm test suspension liquid.Use the asterisk " * " of next-door neighbour's evaluation value to mean 40ppm test suspension liquid.
test A
Spray test suspension liquid to running off a little on tomato sprout.Second day, infect described rice shoot with the spore suspension of Botrytis cinerea germ (Botrytis cinerea) (graw mold of tomato pathogenic former), and cultivate 48h in the saturated atmosphere of 20 ℃, then transfer in the growth room of 24 ℃ and cultivate again 3 days, carry out thereafter visual disease evaluation.
test b
Spray test suspension liquid to running off a little on tomato sprout.Second day, infect described rice shoot with the spore suspension of tomato early blight bacterium (Alternaria solani) (early blight of tomato pathogenic former), and cultivate 48h in the saturated atmosphere of 27 ℃, then transfer in the growth room of 20 ℃ and cultivate 5 days, carry out thereafter visual disease evaluation.
test C
Spray test suspension liquid to running off a little on tomato sprout.Second day, infect described rice shoot with phytophthora infestans (tomato fusarium wilt in late period pathogenic former) spore suspension, and cultivate 24h in the saturated atmosphere of 20 ℃, then moves in the growth room of 20 ℃ and keep 5 days, carries out thereafter visual disease evaluation.
test D
Above spray test suspension liquid to running off a little at creeping bentgrass rice shoot (Agrostis sp.).Second day, infect described rice shoot with wheat bran and the mycelium slurries of redness of the skin or complexion sclerotium germ (Rhizoctonia solani) (turf brown spot pathogenic former), and cultivate 48h in the saturated atmosphere of 27 ℃, then transfer in the growth room of 27 ℃ and cultivate 3 days, carry out thereafter visual disease evaluation.
test E
Spray test suspension liquid to running off a little on the wheat rice shoot.Second day, infect described seedling with the spore suspension of glume blight bacterium (Septoria nodorum) (Septoria grain husk pinta pathogenic former), and cultivate 48h in the saturated atmosphere of 24 ℃, then transfer in the growth room of 20 ℃ and cultivate 9 days, carry out thereafter visual disease evaluation.
test F
Spray test suspension liquid to running off a little on the wheat rice shoot.Second day, infect described rice shoot with the spore suspension of leaf spoting bacteria (Septoria tritici) (wheat leaf spot is caused a disease former), and cultivate 48h in the saturated atmosphere of 24 ℃, then described rice shoot is transferred in the growth room of 20 ℃ and cultivates 19 days again, carries out thereafter visual disease evaluation.
test G
Infect the wheat rice shoot with the spore suspension of Puccinia recondita (Puccinia recondita f.sp.tritici) (wheat leaf rust pathogenic former), and cultivate 24h in the saturated atmosphere of 20 ℃, then transfer in the growth room of 20 ℃ and cultivate 2 days.After the short time drying, be sprayed to the loss point with test suspension liquid, then described rice shoot is moved in 20 ℃ of growth rooms and cultivates 4 days, carry out thereafter visual disease evaluation.
test H
Spray test suspension liquid to running off a little on the wheat rice shoot.Second day, infect described rice shoot with the spore suspension of Puccinia recondita (Puccinia recondita f.sp.tritici) (wheat leaf rust pathogenic former), and cultivate 24h in the saturated atmosphere of 20 ℃, then transfer in the growth room of 20 ℃ and cultivate 6 days, carry out thereafter visual disease evaluation.
test I
Spray test suspension liquid to running off a little on the wheat rice shoot.Second day, infect described rice shoot with the spore pulvis of wheat powdery mildew (be also known as wheat powdery mildew, wheat powdery mildew pathogenic former), and cultivate 8 days in the growth room of 20 ℃, carries out thereafter visual disease evaluation.
Test A-I the results are shown in Table A.In table, grade 100 means 100% disease control, and grade 0 means disease-free control (with respect to tester).Hyphen (-) means without test result.
table A
Figure BDA00002868169001261
Figure BDA00002868169001271
Figure BDA00002868169001291
" Cmpd No. " means compound number.
Mark 1: in previous test, grade is " 65 ".
tested K, L and M
As described below for the regulae generales of tested K, L and M for the preparation test composition.Compound 81, wide-spectrum bactericide, the chloro-6-(2 of 5-, 4, the 6-trifluorophenyl)-7-(4-methyl piperidine-1-yl) [1,2,4] triazol [1,5-a] pyrimidine (BAS600), Cyproconazole, naphthalene pyrrole bacterium amine (isopyrazam), pyrrole metsulfovax, allyl isothiazole, fast promise sweet smell and volution bacterium amine as preparation not, the technical grade material obtains.Fluoxastrobin, Boscalid, tpn, Kocide SD, frost urea cyanogen, Difenoconazole, dimethomorph, epoxiconazole, butadiene morpholine, fluazinam, fludioxonil, folpet, iprodione, Propineb, mancozeb, metalaxyl (being also known as metalaxyl-M), nitrile bacterium azoles, ZEN 90160, the third oxygen quinoline, prothioconazoles, pyraclostrobin, fluorine ether azoles and tricyclazole are as respectively with trade mark AMISTAR, ENDURA, BRAVO, KOCIDE, CURZATE, SCORE, ACROBAT, OPUS, CORBEL, OMEGA, MAXIM, PHALTAN, ROVRAL, MELODY, MANZATE, RIDOMIL GOLD, NOVA, ACANTO, TALIUS, PROLINE, HEADLINE, the formulated product that DOMARK and BEAM sell obtains.At first non-formula materials is dissolved in acetone, then with required concentration (take ppm as unit), is suspended in and comprises the 250ppm surfactant
Figure BDA00002868169001302
the 014(polyol ester) in acetone and purified water (by volume 50/50 mixture).Formula materials is scattered in enough water to obtain required concentration, and in described suspension, does not add organic solvent and surfactant.Then the test mixing thing of gained is used for to tested K, L and M.Spray 200ppm test suspension liquid to running off a little on test plants, be equal to the amount of application of about 800g/ha.To test triplicate, and the mean value of three repetitions will as a result of be reported.
In the synergistic effect existed between two kinds of active components, under the help of Colby formula, set up (referring to Colby, S.R. " Calculating Synergistic and Antagonistic Responses of Herbicide Combinations ", Weeds, (1967), 15,20-22):
p = A + B - [ A &times; B 100 ] .
Use the Colby method, by the activity of two kinds of components based on using separately at first, the active p of prediction that calculates mixture determines the existence of synergistic effect between two kinds of active components.If p is less than the definite effect of test, act synergistically.In above-mentioned formula, the Fungicidally active that A means with degree of control percentage for a kind of component of using separately with amount of application x.The Fungicidally active that the B item means with degree of control percentage for the second component of using with amount of application y.The A that described formula estimation p(uses with amount of application x and the expection Fungicidally active of the mixture of the B used with amount of application y), if their effect sees it is adduction on strict, there do not is interaction.
tested K (being tested K 1, K2, K3, K4, K5)
Spray test suspension liquid to running off a little on the wheat rice shoot.Second day, infect described rice shoot with the spore pulvis of wheat powdery mildew (being also known as the pathogenic former of wheat powdery mildew wheat powdery mildew), and cultivate 7 days in the growth room of 20 ℃, carries out thereafter visual disease evaluation.
test L(tests L1, L2, L3, L4, L5)
Spray test suspension liquid to running off a little on the wheat rice shoot.Second day, infect described rice shoot with the spore suspension of Puccinia recondita (Puccinia recondita f.sp.tritici) (wheat leaf rust pathogenic former), and cultivate 24h in the saturated atmosphere of 20 ℃, then transfer in the growth room of 20 ℃ and cultivate 6 days, carry out thereafter visual disease evaluation.
test M(tests M1, M2, M3, M4, M5)
Spray test suspension liquid to running off a little on the wheat rice shoot.Second day, infect described rice shoot with the spore suspension of leaf spoting bacteria (Septoria tritici) (wheat leaf spot is caused a disease former), and cultivate 48h in the saturated atmosphere of 24 ℃, then described rice shoot is transferred in the growth room of 20 ℃ and cultivates 19 days again, carries out thereafter visual disease evaluation.
The result of tested K-M is present in following table B to K.100 grade shows 100% disease control, and 0 grade shows disease-free control (with respect to tester).Dash (-) means without test result.The hurdle of mark " Obsd " means the average result by three repeated test observations.The hurdle of mark " Exp " means to use for each the Expected Results of the processing mixture of Colby formula calculating.
table B
compound 81 separately and with fast promise sweet smell, allyl isothiazole, mancozeb, iprodione, pyridine acyl the mixture of bacterium amine, Kocide SD, white urea cyanogen or the third oxygen quinoline is for controlling wheat powdery mildew or leaf rust the observation of tick and expected effect
Figure BDA00002868169001321
Figure BDA00002868169001331
Figure BDA00002868169001341
table C
compound 81 separately and with tpn, tricyclazole, fluazinam, dimethomorph, fludioxonil, the mixture of Propineb, metalaxyl-M or folpet is for the observation of controlling wheat powdery mildew or leaf rust tick and expected effect
Figure BDA00002868169001351
Figure BDA00002868169001361
table D
compound 81 separately and with naphthalene pyrrole bacterium amine (isopyrazam), BAS600, broad-spectrum sterilization the mixture of agent, pyrrole metsulfovax, volution bacterium amine, nitrile bacterium azoles or butadiene morpholine is for controlling the wheat white powder the observation of disease or leaf rust tick and expected effect
Figure BDA00002868169001371
table E
compound 81 separately and with Difenoconazole, Fluoxastrobin, fluorine ether azoles, pyraclostrobin, rosickyite bacterium the mixture of azoles, ZEN 90160 or epoxiconazole for the observation of controlling wheat powdery mildew or leaf rust tick and expected effect
Figure BDA00002868169001411
Figure BDA00002868169001421
table F
compound 81 separately and with fast promise sweet smell, Cyproconazole, pyrrole metsulfovax, naphthalene pyrrole bacterium amine (isopyrazam), the mixture of Difenoconazole, Fluoxastrobin or the third oxygen quinoline is for controlling the wheat white powder the observation of disease or leaf rust tick and expected effect
Figure BDA00002868169001422
Figure BDA00002868169001431
Figure BDA00002868169001441
Figure BDA00002868169001451
table G
compound 81 separately and with allyl isothiazole, mancozeb, iprodione, Boscalid, hydrogenthe mixture of copper oxide, white urea cyanogen or tpn is for the observation of controlling wheat powdery mildew or leaf rust tick and expected effect
Figure BDA00002868169001452
Figure BDA00002868169001461
Figure BDA00002868169001471
table H
Compound 81 separately and with the mixture of BAS600, naphthalene pyrrole bacterium amine (isopyrazam), pyrrole metsulfovax, wide-spectrum bactericide or Cyproconazole for the observation of controlling wheat leaf rash spot and expected effect
Figure BDA00002868169001472
Figure BDA00002868169001491
table I
compound 81 separately and with fludioxonil, epoxiconazole, prothioconazoles, Difenoconazole or butadiene morpholine mixture for the observation of controlling wheat leaf rash spot and expected effect
Figure BDA00002868169001492
Figure BDA00002868169001501
table J
compound 81 separately and with pyraclostrobin, tricyclazole, fluazinam, dimethomorph, third gloomy the mixture of zinc, metalaxyl-M, folpet or nitrile bacterium azoles for the observation of controlling wheat leaf rash spot and expected effect
Figure BDA00002868169001511
Figure BDA00002868169001521
Figure BDA00002868169001531
table K
compound 81 separately and with fast promise sweet smell, Fluoxastrobin, ZEN 90160, fluorine ether azoles, volution bacterium amine or the mixture of the third oxygen quinoline for the observation of controlling wheat leaf rash spot and expected effect
Figure BDA00002868169001532
Table B to K shows the present composition of the mixture that comprises representational formula 1 compound and various ingredients (b) compound, shows in some cases the Collaborative Control of wheat powdery mildew, leaf rust tick and leaf rash spot.Can not surpass 100% owing to controlling, the Fungicidally active that the activity increased in mixture surpasses expection not necessarily is observed, but more may observe, with amount of application, provides while significantly being less than 100% control when independent active ingredient components self.Synergy may be not obvious under low amount of application, and wherein independent active ingredient components self has very little activity.Yet, in some cases, for wherein under identical amount of application independent active ingredient components self almost do not have or the combination of non-activity, can observe larger activity.Model, the invention provides for controlling the method for powdery mildew (wheat powdery mildew), leaf rust tick (wheat leaf rust germ) and wheat leaf rash spot (leaf spoting bacteria) as indicated above.
test N1 and N2
Test N1 and N2 relate to assessment compound 81 respectively with the bromo-8-methyl of 2-[(3--6-quinolyl) oxygen]-N-(1,1-dimethyl-2-propine-1-yl)-2-(methyl mercapto) acetamide (compd A 1) and the bromo-6-quinolyl of 2-[(3-) oxygen]-N-(1, the 1-dimethyl ethyl) mixture of butyramide (compd A 2) grows for suppressing leaf spoting bacteria (wheat leaf rash spot pathogenic former).Regulae generales for the preparation test composition is as described below.Compound 81(test N1 and N2), compd A 1(test N1) and compd A 2(test N2) as do not prepare, the acquisition of technical grade material.After the Kong Zhongyu conk medium that at first the test compounds of preparation is not dissolved in DMSO the 96-orifice plate of the conk medium in each hole, to comprise 200 μ L with suitable concentration mixes, provide the concentration (in μ M) of expection.Select the compound concentration scope to cross over from 0 to approaching 100% inhibition field of activity to identify any synergy when leaf spoting bacteria is added the compound treatment combination by use.During the DMSO solution of test compounds was added into hole before adding the conk medium.
Described conk solid culture medium comprises phosphoric acid hydrogen two (3.0g/L) by formation, potassium dihydrogen phosphate (4.0g/L), sodium chloride (0.5g/L), ammonium chloride (1.0g/L), magnesium sulfate 7 hydrate (0.2g) and calcium chloride dihydrate (0.01g/L), and the trace element solution that comprises 1mL/L (manganese sulphate hydrate (0.1mg/mL), ZINC SULFATE HEPTAHYDRATE (0.2mg/mL), copper sulphate (II) pentahydrate (0.2mg/mL), iron sulfate (II) heptahydrate (0.2mg/mL), sodium molybdate dihydrate (0.1mg/mL), cobalt sulphate (II) heptahydrate (0.06mg/mL), also with the former liquor of the vitamin h of 50 μ L/L (0.1mg/mL) prepared by supplementary aqueous mixture for boric acid (0.08mg/mL).Regulate pH to 6.8 with the 1M aqueous sodium carbonate.Described mixture also supplements with the yeast extract of 1g/L, and adds GELRITE gellan gum (Kelco) (4g/L).Add the final volume (as the 900mL volume of conk medium for preparation 1L) of enough water to impel volume to 90%.High steam is processed mixture.When being cooled to 60 ℃, add the rifampin solution (10mg/mL is in DMSO) of the ampicillin aqueous solution (100mg/mL) of the dextrose aqueous solution (10g/L), 500 μ L/L of 100mL/L and 500 μ L/L so that the final volume of conk medium to be provided, then it use during the microlitre pipette is assigned to the hole of 96-orifice plate in still warm.The conk medium distributed in each hole is used the end that distributes pipette to stir so that it is mixed with the DMSO solution that comprises described test compounds.
After conk medium in hole has been cooled to room temperature and solidifies, in each hole, the top surface of growth medium comprises 8 * 10 with 20 μ L 4the suspension of the fungi of individual cell infects.In sterile gauze, dry 2h, after the time, is placed in plate dark incubator 5d under 25 ℃.
Assess conk on the plate reader of setting measurement 600nm illumination absorbance.During the growth inhibition percentage (Obsd.) of observing in test N1 and N2 and the growth inhibition percentage (Exp.) that derives from the expection of using the Colby formula to calculate are listed in respectively table L and M.
table L
compound 81 is independent and withered for controlling leaf as component (b) with the mixture of compd A 1 the observation of germ and expected effect
Figure BDA00002868169001561
Figure BDA00002868169001571
table M
compound 81 is independent and withered for controlling leaf as component (b) with the mixture of compd A 2 the observation of germ and expected effect
Figure BDA00002868169001572
Figure BDA00002868169001581
Compound 81 and compd A 1 provide respectively under the amount of application of 100% inhibition (allowing the collaborative expression increased in inhibition) therein, and under the amount of application that the height that wherein amount of application is not provided respectively by compound 81 and compd A 1 suppresses (as the amount of application of 0.008 μ M of the amount of application of 0.008 or 0.016 μ M of compound 81 and compd A 1) greatly reduces, derive from the compound 81 in test N1 presented in table L and show with observation and the expected result of the mixture of compd A 1 activity (that is, synergy) that is greater than expection.Similarly, compound 81 and compd A 2 provide respectively under the amount of application of 100% inhibition therein, and, under the amount of application that the height that wherein amount of application is not provided respectively by compound 81 and compd A 2 suppresses (as the amount of application of 0.8 μ M of the amount of application of 0.008 or 0.016 μ M of compound 81 and compd A 2) greatly reduces, derive from the compound 81 in test N2 presented in table M and show with observation and the expected result of the mixture of compd A 2 activity that is greater than expection.

Claims (20)

1. Fungicidal composition comprises:
(a) at least one compound, described compound is selected from compound, its N-oxide and salt thereof of formula 1:
Wherein
X is CHOH, O or NH;
R 1for halogen or methyl;
R 2for H, cyano group, halogen or C 1-C 2alkoxyl;
R 3for H, halogen or methyl;
R 4for halogen;
R 5for H, cyano group, halogen or C 1-C 2alkoxyl; And
R 6for H or halogen; With
(b) at least one additional Fungicidal compounds.
2. composition according to claim 1, the compound or its salt that wherein component (a) comprises formula 1, wherein in formula 1,
R at most only 2and R 3in one be H; And
R at most only 5and R 6in one be H.
3. composition according to claim 2, wherein in formula 1,
R 1for F, Cl or Br;
R 2for H, cyano group, F, Cl, Br or methoxyl group;
R 3for H, F or Cl;
R 4for F, Cl or Br;
R 5for H, cyano group, F, Cl or methoxyl group; And
R 6for H or F.
4. composition according to claim 3, wherein in formula 1,
R 3for H or F; And
R 5for cyano group, F, Cl or methoxyl group.
5. composition according to claim 1, wherein component (a) comprises and is selected from following compound:
N, two (the chloro-4-fluorophenyls of 2-)-1 of 4-, 3-dimethyl-1H-pyrazoles-5-amine,
N-(2-is bromo-4, the 6-difluorophenyl)-4-(2, the 4-difluorophenyl)-1,3-dimethyl-1H-pyrazoles-5-amine,
N-(2-is bromo-4, the 6-difluorophenyl)-the bromo-4-fluorophenyl of 4-(2-)-1,3-dimethyl-1H-pyrazoles-5-amine,
N-(2-is bromo-4, the 6-difluorophenyl)-the chloro-4-fluorophenyl of 4-(2-)-1,3-dimethyl-1H-pyrazoles-5-amine,
N-(4-chloro-2,6-difluoro phenyl) the chloro-4-fluorophenyl of-4-(2-)-1,3-dimethyl-1H-pyrazoles-5-amine,
The chloro-2-fluorophenyl of 4-[5-[(4-) amino]-1,3-dimethyl-1H-pyrazoles-4-yl]-3, the 5-difluorobenzonitrile,
N-(2-is chloro-4, the 6-difluorophenyl)-the chloro-4-fluorophenyl of 4-(2-)-1,3-dimethyl-1H-pyrazoles-5-amine,
4-[5-[(2-is chloro-4, the 6-difluorophenyl) amino]-1,3-dimethyl-1H-pyrazoles-4-yl]-the 3-fluorobenzonitrile,
The chloro-4-fluorophenyl of 4-[[4-(2-)-1,3-dimethyl-1H-pyrazoles-5-yl] oxygen]-3, the 5-difluorobenzonitrile,
The chloro-4-fluorophenyl of 4-(2-)-N-(2, the chloro-6-fluorophenyl of 4-bis-)-1,3-dimethyl-1H-pyrazoles-5-amine,
The chloro-4-fluorophenyl of 4-(2-)-N-(2, the fluoro-4-anisyl of 6-bis-)-1,3-dimethyl-1H-pyrazoles-5-amine,
The chloro-4-fluorophenyl of 4-(2-)-α-(2,4-difluorophenyl)-1,3-dimethyl-1H-pyrazoles-5-methyl alcohol,
N-(2, the chloro-6-fluorophenyl of 4-bis-)-4-(2, the 4-difluorophenyl)-1,3-dimethyl-1H-pyrazoles-5-amine,
4-(2, the 4-dichlorophenyl)-N-(2, the 4-difluorophenyl)-1,3-dimethyl-1H-pyrazoles-5-amine,
4-(2, the fluoro-4-anisyl of 6-bis-)-1,3-dimethyl-N-(2,4,6-trifluorophenyl)-1H-pyrazoles-5-amine,
4-[[1,3-dimethyl-4-(2,4,6-trifluorophenyl)-1H-pyrazoles-5-yl] oxygen]-3, the 5-difluorobenzonitrile,
The chloro-4-fluorophenyl of 4-(2-)-chloro-6-fluorophenyl of N-(2-)-1,3-dimethyl-1H-pyrazoles-5-amine,
The bromo-4-fluorophenyl of 4-(2-)-chloro-6-fluorophenyl of N-(2-)-1,3-dimethyl-1H-pyrazoles-5-amine,
The bromo-6-fluorophenyl of N-(2-)-chloro-4-fluorophenyl of 4-(2-)-1,3-dimethyl-1H-pyrazoles-5-amine,
The bromo-4-fluorophenyl of 4-(2-)-bromo-6-fluorophenyl of N-(2-)-1,3-dimethyl-1H-pyrazoles-5-amine,
The bromo-6-fluorophenyl of N-(2-)-4-(2, the 4-difluorophenyl)-1,3-dimethyl-1H-pyrazoles-5-amine,
The bromo-6-fluorophenyl of N-(2-)-4-(2, the 6-difluorophenyl)-1,3-dimethyl-1H-pyrazoles-5-amine,
The chloro-4-fluorophenyl of 4-(2-)-fluoro-6-aminomethyl phenyl of N-(2-)-1,3-dimethyl-1H-pyrazoles-5-amine,
The chloro-4-fluorophenyl of 4-(2-)-chloro-6-aminomethyl phenyl of N-(2-)-1,3-dimethyl-1H-pyrazoles-5-amine,
The bromo-6-aminomethyl phenyl of N-(2-)-chloro-4-fluorophenyl of 4-(2-)-1,3-dimethyl-1H-pyrazoles-5-amine,
The chloro-6-aminomethyl phenyl of N-(2-)-fluoro-4-anisyl of 4-(2-)-1,3-dimethyl-1H-pyrazoles-5-amine,
The bromo-6-aminomethyl phenyl of N-(2-)-fluoro-4-anisyl of 4-(2-)-1,3-dimethyl-1H-pyrazoles-5-amine,
The fluoro-4-anisyl of 4-(2-)-fluoro-6-aminomethyl phenyl of N-(2-)-1,3-dimethyl-1H-pyrazoles-5-amine,
The chloro-6-fluorophenyl of N-(2-)-fluoro-4-anisyl of 4-(2-)-1,3-dimethyl-1H-pyrazoles-5-amine,
The bromo-6-fluorophenyl of N-(2-)-fluoro-4-anisyl of 4-(2-)-1,3-dimethyl-1H-pyrazoles-5-amine,
The chloro-4-anisyl of 4-(2-)-chloro-6-aminomethyl phenyl of N-(2-)-1,3-dimethyl-1H-pyrazoles-5-amine,
The bromo-6-aminomethyl phenyl of N-(2-)-chloro-4-anisyl of 4-(2-)-1,3-dimethyl-1H-pyrazoles-5-amine,
The bromo-6-aminomethyl phenyl of N-(2-)-chloro-4-anisyl of 4-(2-)-1,3-dimethyl-1H-pyrazoles-5-amine,
The bromo-6-aminomethyl phenyl of N-(2-)-4-(2, the 4-difluorophenyl)-1,3-dimethyl-1H-pyrazoles-5-amine,
The bromo-4-fluorophenyl of 4-(2-)-bromo-6-aminomethyl phenyl of N-(2-)-1,3-dimethyl-1H-pyrazoles-5-amine,
The bromo-4-fluorophenyl of 4-(2-)-fluoro-6-aminomethyl phenyl of N-(2-)-1,3-dimethyl-1H-pyrazoles-5-amine,
4-(2, the 4-difluorophenyl)-the fluoro-6-aminomethyl phenyl of N-(2-)-1,3-dimethyl-1H-pyrazoles-5-amine,
The chloro-6-aminomethyl phenyl of N-(2-)-4-(2, the 4-difluorophenyl)-1,3-dimethyl-1H-pyrazoles-5-amine,
4-(2, the 4-difluorophenyl)-N-(2, the 6-3,5-dimethylphenyl)-1,3-dimethyl-1H-pyrazoles-5-amine,
The chloro-4-fluorophenyl of 4-(2-)-N-(2, the 6-3,5-dimethylphenyl)-1,3-dimethyl-1H-pyrazoles-5-amine,
The bromo-6-fluorophenyl of N-(2-)-chloro-4-anisyl of 4-(2-)-1,3-dimethyl-1H-pyrazoles-5-amine,
The chloro-6-fluorophenyl of N-(2-)-4-(2,4-difluorophenyl)-1,3-dimethyl-1H-pyrazoles-5-amine and
The bromo-4-fluorophenyl of 4-(2-)-chloro-6-aminomethyl phenyl of N-(2-)-1,3-dimethyl-1H-pyrazoles-5-amine.
6. according to the described composition of any one in claim 1 to 5, wherein component (b) comprises at least one and is selected from following Fungicidal compounds:
(b1) benzimidazole methyl carbamate fungicide;
(b2) dicarboximide fungicide;
(b3) demethylation inhibitor fungicide;
(b4) phenyl amide fungicide;
(b5) amine/morpholine fungicide;
(b6) phosphatide biosynthesis inhibitor fungicide;
(b7) carboxylic acid amides fungicide;
(b8) hydroxyl (2-amino-) pyrimidine fungicide;
(b9) aniline pyrimidine fungicide;
(b10) N-carbanilate fungicide;
(b11) the outside inhibitor fungicide of quinone;
(b12) phenylpyrrole fungicide;
(b13) quinoline fungicide;
(b14) class lipid peroxidation inhibitor fungicide;
(b15) melanocyte biosynthesis inhibitor-reductase fungicide;
(b16) melanocyte biosynthesis inhibitor-dehydratase fungicide;
(b17) hydroxyanilines fungicide;
(b18) squalene-inhibitors of cyclooxygenases fungicide;
(b19) polyoxin fungicide;
(b20) phenylurea fungicide;
(b21) the inner inhibitor fungicide of quinone;
(b22) benzamide fungicide;
(b23) enol pyranose aldehydic acid antibiotic fungicide;
(b24) own pyrans glycosyl antibiotic fungicide;
(b25) glycopyranosyl antibiotic: protein synthesis of antifungal agents;
(b26) glycopyranosyl antibiotic: trehalase and inositol biosynthesis fungicide;
(b27) cyanoacetamide oxime fungicide;
(b28) carbamate fungicide;
(b29) the even fungicide of oxidative phosphorylation solution;
(b30) organotin fungicide;
(b31) carboxylic acid fungicide;
(b32) heteroaromatic fungicide;
(b33) phosphonate ester fungicide;
(b34) phthalamidic acid fungicide;
(b35) phentriazine fungicide;
(b36) benzene-sulfonamide fungicide;
(b37) pyridazinone fungicide;
(b38) thiophene-carboxylic acid amides fungicide;
(b39) pyrimidine acid amides fungicide;
(b40) carboxylic acid amide fungicide;
(b41) tetracycline antibiotic fungicide;
(b42) thiocarbamate fungicide;
(b43) benzamide fungicide;
(b44) host plant defence induction type fungicide;
(b45) multidigit point contact active fungicide;
(b46) Fungicidal compounds, described Fungicidal compounds is not the Fungicidal compounds of component (a) and component (b1) to (b45); And (b1) to the salt of the compound of (b46).
7. composition according to claim 6, wherein component (b) comprises at least one Fungicidal compounds, and described Fungicidal compounds is from being selected from (b1) to (b46) two not each group on the same group.
8. composition according to claim 1, wherein component (b) comprises at least one and is selected from following compound: diazosulfide-S-methyl, cartap, hot azoles mepanipyrim (ametoctradin), amisulbrom, anilazine, penta ring azoles, Fluoxastrobin, M 9834, M 9834-M, benodanil, benomyl, the benzene metsulfovax, the cumene metsulfovax, diclomezin, binapacryl, biphenyl, Bitertanol, wide-spectrum bactericide, blasticidin S-S, Boscalid, bromuconazole, bupirimate, carboxin, ring propionyl bacterium amine, difoltan, captan, carbendazim, chloroneb, tpn, chlozolinate, clotrimazole, mantoquita, the match seat goes out, cyflufenamid, frost urea cyanogen, Cyproconazole, cyprodinil, Euparen, two chlorine zarilamids, diclomezine, botran, the mould prestige of second, Difenoconazole, the difluoro woods, Milcurb, dimethomorph, dimoxystrobin, alkene azoles alcohol, alkene azoles alcohol-M, karathane, the Delan, dodemorph, dodine, edifenphos, Enestroburin, epoxiconazole, Guardian, the phonetic phenol of second, Grandox fumigant,
Figure FDA00002868168900071
cycloheximide triazole, Fenamidone, Fenarimol, RH-7592, first furan anilide, fenhexamid, zarilamid, fenpiclonil, fenpropidin, butadiene morpholine, amine benzene pyrrole bacterium ketone, fentin acetate, triphenyl tin chloride, triphenyl tin hydroxide, ferbam, ferimzone, fluazinam, fludioxonil, fluorine acyl bacterium amine, flumorph, fluopicolide, fluorine pyrrole bacterium acid amides, the fluorine acid imide, fluoxastrobin, Fluquinconazole, Flusilazole, flusulfamide, fluorine thiophene bacterium is clean, flutolanil, Flutriafol, fluorobenzene pyrrole bacterium amine (fluxapyroxad), folpet, phosethyl-Al, furidazol, furalaxyl, good fortune Lapie, own azoles alcohol, dislike mould spirit, gram heat is clean, imazalil, the acid amides azoles, iminoctadine, iodo propinyl butyl carbamate, plant the bacterium azoles, iprobenfos, iprodione, Propineb, Isoprothiolane, naphthalene pyrrole bacterium amine (isopyrazam), isotianil, kasugarnycin, gram is received glad, mancozeb, mandipropamid, maneb, mebenil, dinocap, metalaxyl, metalaxyl-M, metconazole, methasulfocarb, Carbatene, SSF 126, mepanipyrim, metrafenone, nitrile bacterium azoles, how to replace fragrant, Neo-Asozin (ferric methylarsonate), nuarimol, octhilinone, ofurace, orysastrobin, Wakil,
Figure FDA00002868168900072
quinoline acid, imidazoles, oxycarboxin, oxytetracycline, penconazole, Pencycuron, penta benzene pyrrole bacterium amine, the pyrrole metsulfovax, pefurazoate, phosphorous acid and salt thereof, phthalide, ZEN 90160, pipron, polyoxin, allyl isothiazole, prochloraz, procymidone, Propamocarb, Propamocarb-hydrochloride, propiconazole, Propineb, the third oxygen quinoline, prothiocarb, prothioconazoles, pyraclostrobin, azoles amine bacterium ester, azoles bacterium ester, Ppyrazophos, pyrrole bacterium benzene prestige (pyribencarb), pyributicarb, pyrifenox, phonetic mould amine, methoxy benzene pyridine bacterium (pyriofenone), pyroquilon, pyrrolnitrin, chinomethionat, fast promise sweet smell, pcnb, encircle the third pyrrole bacterium amine (sedaxane), Silthiopham, simeconazoles, volution bacterium amine, streptomycin, sulphur, Tebuconazole, isobutyl ethoxyquin (tebufloquin), gram is withered rotten, tecnazene, Terbinafine, fluorine ether azoles, probenazole, the thiophene furan goes out, topsin, thiophanate-methyl, arasan, tiadinil, tolelofos-methyl, tolyfluanid, triazolone, Triadimenol, azoles bacterium piperazine, tricyclazole, tridemorph, fluorine bacterium azoles, tricyclazole, oxime bacterium ester, triforine, Trimorfamid Fademorf, triticonazole, uniconazole P, jinggangmeisu, downy mildew goes out, vinclozolin, zineb, ziram, oxamides, the chloro-3-(trifluoromethyl of N'-[4-[4-) phenoxy group]-2, the 5-3,5-dimethylphenyl]-N-ethyl-N-methyl azomethine acid amides, the chloro-6-(2 of 5-, 4,6-trifluorophenyl)-7-(4-methyl piperidine-1-yl) [1,2,4] triazols [1,5-a] pyrimidine, the N-[2-[4-[[3-(4-chlorphenyl)-2-propine-1-yl] oxygen]-the 3-anisyl] ethyl]-3-methyl-2-[(methylsulfonyl) amino] butyramide, the N-[2-[4-[[3-(4-chlorphenyl)-2-propine-1-yl] oxygen]-the 3-anisyl] ethyl]-3-methyl-2-[(ethylsulfonyl) amino] butyramide, the iodo-3-propyl group of 2-butoxy-6--4H-1-benzopyran-4-one, the 3-[5-(4-chlorphenyl)-2,3-dimethyl-3-is different
Figure FDA00002868168900081
azoles quinoline base] pyridine, the N-[1-[[[1-(4-cyano-phenyl) ethyl] sulfonyl] methyl] propyl group] carbamic acid-4-fluorobenzene ester, the N-[[(cyclo propyl methoxy) amino] [the 6-(difluoro-methoxy)-2, the 3-difluorophenyl] methylene] phenyl acetamide, α-(methoxyimino)-N-methyl-2-[[[1-[3-(trifluoromethyl) phenyl] ethyoxyl] imino group] methyl] phenyl acetamide, the chloro-3-(trifluoromethyl of N'-[4-[4-) phenoxy group]-2, the 5-3,5-dimethylphenyl]-N-ethyl-N-methyl azomethine acid amides, the chloro-2-nitrobenzophenone of N-(4-)-N-ethyl-4-methyl benzenesulfonamide, 2-[[[[3-(2, the 6-dichlorophenyl)-1-methyl-2-propylene-1-subunit] amino] oxygen] methyl]-α-(methoxyimino)-N--methylbenzene acetamide, 1-[(2-propylene sulfenyl) carbonyl]-the 2-(1-Methylethyl)-the 4-(2-aminomethyl phenyl)-5-amino-1H-pyrazoles-3-ketone, 5-ethyl-6-octyl group-[1, 2, 4] triazol [1, 5-a] pyrimidin-7-ylamine, N-[4-[[[[(1-methyl isophthalic acid H-tetrazolium-5-yl) phenylmethylene] amino] oxygen] methyl]-the 2-thiazolyl] amyl carbamate and N-[6-[[[[(1-methyl isophthalic acid H-tetrazolium-5-yl) phenylmethylene] amino] oxygen] methyl]-the 2-pyridine radicals] amyl carbamate.
9. composition according to claim 1, wherein component (b) comprises at least one Fungicidal compounds, and described Fungicidal compounds is selected from compound and the salt thereof of formula A1
Figure FDA00002868168900082
Wherein
R a1for halogen, C 1-C 4alkoxyl or C 1-C 4alkynyl;
R a2for H, halogen or C1-C 4alkyl;
R a3for C 1-C 12alkyl, C 1-C 12haloalkyl, C 1-C 12alkoxyl, C 2-C 12alkoxyalkyl, C 2-C 12thiazolinyl, C 2-C 12alkynyl, C 4-C 12alkoxyl thiazolinyl, C 4-C 12alkoxyl alkynyl, C 1-C 12alkylthio group or C 2-C 12alkylthio alkyl;
R a4for methyl or Y a1-R a5;
R a5for C 1-C 2alkyl; And
Y a1for CH 2, O or S.
10. composition comprises: (a) at least one compound, and described compound is selected from compound, its N oxide and salt thereof of formula 1 as defined in claim 1; Control compound or reagent with at least one invertebrate pests.
11. composition, the composition that comprises any one in claim 1 to 10 and at least one annexing ingredient, described annexing ingredient is selected from surfactant, solid diluent and liquid diluent.
12. the method for the disease that protective plant or plant seed are avoided being caused by fungal pathogens, comprise the composition of using any one in the claim 1 to 11 of antifungal effective dose to plant or plant seed.
13. protective plant is avoided the method for powdery mildew disease; comprise composition from any one in the claim 1 to 5 of antifungal effective dose to plant that use, wherein component (b) comprises the Fungicidal compounds that at least one is selected from the outside inhibitor fungicide of (b11) quinone.
14. protective plant is avoided the method for Septoria disease, comprises composition from the claim 9 of antifungal effective dose to plant that use.
15. the compound of formula 1 or its N-oxide or its salt,
Figure FDA00002868168900091
Wherein
X is NH;
R 1for halogen or methyl;
R 2for H;
R 3for halogen or methyl;
R 4for halogen;
R 5for H, cyano group, halogen or C 1-C 2alkoxyl; And
R 6for H or halogen;
Precondition is to work as R 1during for F, R 3for Cl, and work as R 1during for Cl, R 3for F.
16. compound according to claim 15, wherein
R 3for F or Cl.
17. compound according to claim 16, wherein
R 1for Cl or Br; And
R 3for F.
18. compound according to claim 15, described compound is selected from:
The chloro-4-fluorophenyl of 4-(2-)-chloro-6-fluorophenyl of N-(2-)-1,3-dimethyl-1H-pyrazoles-5-amine,
The bromo-4-fluorophenyl of 4-(2-)-chloro-6-fluorophenyl of N-(2-)-1,3-dimethyl-1H-pyrazoles-5-amine and
The bromo-6-fluorophenyl of N-(2-)-chloro-4-fluorophenyl of 4-(2-)-1,3-dimethyl-1H-pyrazoles-5-amine.
19. Fungicidal composition comprises: the compound of any one in (1) claim 15 to 18; (2) at least one annexing ingredient, described annexing ingredient is selected from surfactant, solid diluent and liquid diluent.
20. the method for the disease that protective plant or plant seed are avoided being caused by fungal pathogens, comprise the compound of using any one in the claim 15 to 18 of antifungal effective dose to plant or plant seed.
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